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CN108975494B - Method for treating black smelly water by using graphene modified straw material - Google Patents

Method for treating black smelly water by using graphene modified straw material Download PDF

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CN108975494B
CN108975494B CN201811025594.6A CN201811025594A CN108975494B CN 108975494 B CN108975494 B CN 108975494B CN 201811025594 A CN201811025594 A CN 201811025594A CN 108975494 B CN108975494 B CN 108975494B
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graphene
sludge
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water
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CN108975494A (en
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张雯
任小慧
董月
张振
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Biodiversity & Conservation Biology (AREA)
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  • Biological Treatment Of Waste Water (AREA)
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Abstract

一种石墨烯改性秸秆材料处理黑臭水的方法，其主要是将洗净干燥后的玉米秸秆切成大小均匀块状，用去离子水洗净后烘干备用；然后浸泡于盐酸溶液中，于50℃‑60℃条件下在恒温水浴锅中反应1‑2h，将秸秆块取出，水洗、干燥，用氧化石墨烯溶液浸泡上述处理好的秸秆材料，48h后洗涤3次，自然风干；用海藻酸钠溶液常温下浸泡无破损的上述石墨烯改性秸秆块，32h后洗涤风干；将制备好的石墨烯秸秆块浸泡在驯化好的污泥中进行曝气处理，待载体表面生成污泥状的生物膜为止，然后将投加挂膜后的石墨烯改性秸秆材料应用于黑臭废水的处理。本发明处理效率高、成本低、操作简单易控、对水质变化稳定性强，载体材料可重复利用。A method for treating black and odorous water with a graphene-modified straw material, which mainly comprises cutting the cleaned and dried corn stalks into blocks of uniform size, washing with deionized water, and drying for subsequent use; then soaking in a hydrochloric acid solution , react in a constant temperature water bath for 1-2 h under the condition of 50 ℃-60 ℃, take out the straw block, wash with water, dry, soak the above-treated straw material with graphene oxide solution, wash 3 times after 48 h, and air dry naturally; Soak the undamaged graphene-modified straw blocks in sodium alginate solution at room temperature, wash and air-dry after 32 hours; soak the prepared graphene straw blocks in the domesticated sludge for aeration treatment, and wait until the surface of the carrier is polluted. Mud-like biofilm, and then the graphene-modified straw material after adding the film was applied to the treatment of black and odorous wastewater. The invention has high treatment efficiency, low cost, simple and easy-to-control operation, strong stability to water quality changes, and the carrier material can be reused.

Description

Method for treating black smelly water by using graphene modified straw material
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating smelly black water.
Background
The black smelly water is an extreme state of organic pollution of water and has the characteristics of blackening and smelling, organic matter putrefaction, decomposition, fermentation and difficult degradation. In spite of the current black and odorous water pollution situation, an effective wastewater treatment technology is urgently needed, and traditional physical and chemical methods such as dredging, sewage interception, direct aeration, flocculation, adsorption and the like have poor effects in black and odorous water treatment, are high in cost and are easy to cause secondary pollution. The biological treatment technology is widely applied at present, can decompose and convert organic matters into stable inorganic matters, is economic and efficient, has no secondary pollution, has good sewage purification effect, can be combined with other methods to comprehensively treat the pollution, and has great development potential. Research on treating black and odorous water by biological complex enzyme sewage purifying agent of Wang hong Jun et al (Wang hong Jun, Hu Ju Xiang, Wu Sheng Gui, etc.)]Water conservancy fishery, 2007,27(1):68-70) treats black and odorous water body through biological complex enzyme, BOD when the enzyme concentration is 6mg/L5、COD、S2-、NH3The highest degradation rate is obtained by-N and the like, and the black and odorous phenomenon is eliminated. Research on the use of effective microbial flora for repairing river contaminated by Renwei et al (Renwei, Liusheng Scale, etc. [ J ]]Zhejiang water conservancy and hydropower specialty school bulletin 2008,18(2):41-43) adding efficient composite bacteria EM into polluted river, COD, N, P and the like in river water are effectively degraded, transparency is improved, and black and odorous state is achievedTo solve the problem.
Common biological treatment technologies at home and abroad, such as activated sludge, Membrane Bioreactors (MBR), aerobic and anaerobic bioreactors, trickling filters, enzyme treatment, biological adsorption and the like, have achieved remarkable results at present, but the disadvantages of high cost, complex operation, weak toxicity bearing capacity and the like are undeniable to a greater or lesser extent. The immobilized microorganism technology can maintain the high density and biological activity functions of strains, can proliferate under proper conditions, and biodegrade and adsorb organic compounds in water.
The currently used immobilization support materials are roughly classified into inorganic supports and organic supports. The inorganic carrier mainly comprises activated carbon, diatomite and the like, has good strength, is simple to prepare and operate, but has weak absorption on microorganisms. The organic materials are mainly divided into two types of natural polymer materials and artificially synthesized polymer materials: the former mainly comprises agar, sodium alginate and the like, has no toxic action on microorganisms, but has lower mechanical strength, is easy to decompose thalli and has shorter service life; the other is polystyrene, polyvinyl alcohol and other materials which have good mechanical properties and long service life but are unfavorable to the activity of microorganisms.
The invention content is as follows:
the invention aims to provide a method for treating black and odorous water by using a graphene modified straw material, which has the advantages of high treatment efficiency, low cost, simple and easily-controlled operation, strong stability on water quality change, reusability of a carrier material and no secondary pollution.
The method of the invention comprises the following steps:
(1) preparation of graphene modified straw material
Cutting cleaned and dried corn straws into blocks with uniform sizes, cleaning the corn straws with deionized water, and drying the corn straws for later use; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 50-60 ℃ for 1-2h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a blast drying oven at 30-40 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the water bath condition of 40-50 ℃, washing for 3 times by using deionized water after 48 hours, and naturally drying; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material;
(2) the method for treating black smelly water by using the graphene modified straw material comprises the following steps:
firstly, domesticating activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the prepared graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding riverway black odorous water into a treatment tank with an aeration device, adjusting the pH value of the black odorous water to 7.0, and adding graphene modified straw materials subjected to film hanging in a proportion that 100 pieces of graphene modified straw materials are added per liter of black odorous water; the temperature of the treatment tank is kept at 25-30 ℃ by adopting a heating device, DO is kept at 1.5-2.5 mg/L by an aeration device, the aeration treatment is carried out for 72 hours, the COD degradation rate of the effluent is 85-95%, and the ammonia nitrogen value is 10-15 mg/L;
and the used graphene modified straw material is re-immersed into the domesticated sludge for continuous film formation, and can be repeatedly reused until the carrier material is damaged.
The corn stalk material used in the invention mainly comprises natural polymers such as cellulose, hemicellulose and the like, a large number of active groups such as hydroxyl, carboxyl, methoxyl, conjugated double bonds and the like are distributed on a molecular chain, and the interior of the molecular chain has obvious pore passages, so that the corn stalk material has good complexing adsorption and flocculation effects on pollutants in water. However, the mechanical properties of the straw carrier are general, and after the straw carrier is treated by the graphene oxide material, the straw carrier has a large number of active groups such as hydroxyl, carboxyl and epoxy groups, and has good chemical stability, strong hydrophilic performance and pollution resistance. The graphene oxide has a mesh channel formed by hydrogen bonds and the like inside, so that the graphene oxide is good in stability and has a strong adsorption effect.
Compared with the prior art, the invention has the following advantages:
1. the preparation method is simple and easy to implement, and the corn straw material is a common agricultural and forestry waste resource, is cheap and easy to obtain, and has low cost.
2. The immobilized microorganism technology keeps high activity and high concentration of microorganisms in a reaction device, achieves the effect of biological synergism, simultaneously weakens the impact and toxic action of toxic pollutants on the microorganisms due to the high density of the microorganisms and the blocking of an immobilized carrier, and the quantity of the immobilized biological dry film is 0.4-0.8 g/g of the carrier which is more than 4 times that of a common carrier.
3. The graphene modified straw material has good biocompatibility, strong adsorbability and surface active groups, can quickly fix and degrade mixed bacteria to promote the growth of microorganisms, and is easy to separate solid from liquid and high in impact load resistance.
4. The graphene modified straw material has the advantages of strong mechanical property, strong reproducibility, simple regeneration method, repeated utilization for many times, reduction of sewage treatment cost, no secondary pollution, applicability to long-term batch operation in actual production and great potential in black and odorous water treatment.
5. Compared with the common biological method for treating the stinky black water, the high-concentration black stinky wastewater can pass through the treatment device, the degradation rate of the COD value of the effluent reaches more than 85 percent, and the ammonia nitrogen value basically reaches the discharge standard of the national first-level standard of 15 mg/L.
Detailed Description
Example 1
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 50 ℃ for 1.5h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven at 35 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the water bath condition of 45 ℃, washing the straw material for 3 times by using deionized water after 48 hours, and naturally drying the straw material; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge with black and odorous wastewater: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river by 20 times, 15 times, 10 times, 5 times and 2 times without diluting; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 7.0, adding 400 pieces of graphene modified straw materials after film formation, keeping the temperature of the treatment tank at 30 ℃ by adopting a heating device, keeping DO at 1.5-2.5 mg/L by the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 95%, and the ammonia nitrogen value is 10 mg/L.
Example 2
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 55 ℃ for 1h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven at 30 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the condition of water bath at 50 ℃, washing for 3 times by using deionized water after 48 hours, and naturally drying; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river course by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 7.0, adding 800 pieces of graphene modified straw materials after film formation, keeping the temperature of the treatment tank at 30 ℃ by adopting a heating device, keeping DO at 1.5-2.5 mg/L by the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 90%, and the ammonia nitrogen value is 15 mg/L.
Example 3
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 60 ℃ for 1.5h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in an air drying oven at 40 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the water bath condition of 45 ℃, washing the straw material for 3 times by using deionized water after 48 hours, and naturally drying the straw material; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river course by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 6.0, adding 400 pieces of graphene modified straw materials after film formation, keeping the temperature of the treatment tank at 30 ℃ by adopting a heating device, keeping DO at 1.5-2.5 mg/L by the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 85%, and the ammonia nitrogen value is 15 mg/L.
Example 4
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 52 ℃ for 2h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven at 38 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the condition of water bath at 40 ℃, washing for 3 times by using deionized water after 48 hours, and naturally drying; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge taken from a sewage treatment plant for 8h, standing for 30min, fishing out suspended substances, discharging supernatant, and diluting the black and odorous wastewater in the river by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 8.0, adding 600 pieces of graphene modified straw materials after film formation, keeping the temperature of the treatment tank at 30 ℃ by adopting a heating device, keeping DO at 1.5-2.5 mg/L by the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 88%, and the ammonia nitrogen value is 10 mg/L.
Example 5
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 56 ℃ for 1h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven at 32 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the water bath condition of 48 ℃, washing the straw material for 3 times by using deionized water after 48 hours, and naturally drying the straw material; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river course by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 7.0, adding 500 pieces of graphene modified straw materials after film formation, keeping the temperature of the treatment tank at 35 ℃ by adopting a heating device, keeping DO at 1.5-2.5 mg/L by the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 95%, and the ammonia nitrogen value is 10 mg/L.
Example 6
Cutting cleaned and dried corn straws into blocks with uniform sizes: washing with deionized water, and drying for use, wherein r is 7mm, and h is 4 mm; soaking the treated straw blocks in 0.5mol/L hydrochloric acid solution, reacting in a constant-temperature water bath kettle at 58 ℃ for 2h, taking out the straw blocks, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven at 33 ℃; soaking the treated straw material in a graphene oxide solution with the concentration of 2.4mg/mL under the condition of 42 ℃ water bath, washing for 3 times by using deionized water after 48 hours, and naturally drying; soaking the undamaged graphene modified straw material in a sodium alginate solution with the concentration of 1.8%, washing the straw material with deionized water for 3 times after 32 hours, and naturally drying the straw material to obtain the graphene modified straw material;
domesticating the activated sludge by using black and odorous wastewater, wherein the domesticating method comprises the following steps: aerating the sludge for 8h after the sludge is taken from a sewage treatment plant, standing for 30min, fishing out suspended substances, and discharging supernatant. Diluting the black and odorous wastewater in the river course by 20 times, 15 times, 10 times, 5 times, 2 times or not; adding the black and odorous wastewater with the lowest concentration into activated sludge (the volume ratio is 2: 1), aerating for 48 hours to keep DO in the sludge between 1.5-2.5 mg/L all the time, then standing and precipitating for 30min, and discharging supernatant; then gradually increasing the concentration of the black and odorous wastewater, repeating the process, and finally continuously aerating for 24 hours and observing the sludge activity recovery condition until the activated sludge is in a black brown flocculent state, quickly separating mud from water during static sedimentation, compacting a sludge layer and clearing supernatant fluid, wherein the domestication can be considered to be successful; then, soaking the graphene straw material in the domesticated sludge, stirring, and carrying out aeration treatment until a sludge-like biological film is generated on the surface of the carrier;
adding 4L of riverway black and odorous water into an 8L organic glass treatment tank with an aeration device, adjusting the pH value of the black and odorous water to 7.0, adding 800 pieces of graphene modified straw materials after film formation, treating at room temperature of 25 ℃, keeping DO between 1.5 and 2.5mg/L through the aeration device, and carrying out aeration treatment for 72 hours, wherein the COD degradation rate of effluent is 85 percent, and the ammonia nitrogen value is 10 mg/L.

Claims (4)

1.一种使用新型石墨烯改性秸秆材料处理黑臭废水方法，其特征在于：1. a method for treating black and odorous wastewater using novel graphene-modified straw material, is characterized in that: (1)石墨烯改性秸秆材料的制备(1) Preparation of graphene-modified straw materials 将洗净干燥后的玉米秸秆切成大小均匀块状，用去离子水洗净后烘干备用；将上述处理好的秸秆块浸泡于0.5mol/L的盐酸溶液中，于50-60℃条件下在恒温水浴锅中反应1-2h，将秸秆块取出，用蒸馏水洗至滤液呈中性，于30-40℃鼓风干燥箱内干燥；用浓度为2.4mg/mL的氧化石墨烯溶液，在40-50℃水浴条件下浸泡上述处理好的秸秆材料，48h后用去离子水洗涤3次，自然风干；用浓度为1.8％的海藻酸钠溶液浸泡无破损的上述石墨烯改性秸秆材料，32h后用去离子水洗涤3次，自然风干；Cut the washed and dried corn stalks into blocks of uniform size, wash them with deionized water, and then dry them for later use; soak the above-treated straw blocks in a 0.5mol/L hydrochloric acid solution, at 50-60°C React in a constant temperature water bath for 1-2 h, take out the straw pieces, wash with distilled water until the filtrate is neutral, and dry in a blast drying oven at 30-40 °C; use a graphene oxide solution with a concentration of 2.4 mg/mL, Soak the above-mentioned treated straw materials in a water bath at 40-50 °C, wash three times with deionized water after 48 hours, and air dry naturally; soak the above-mentioned graphene-modified straw materials without damage in a sodium alginate solution with a concentration of 1.8% , washed 3 times with deionized water after 32h, and air-dried naturally; (2)使用上述石墨烯改性秸秆材料处理黑臭水的方法：(2) use above-mentioned graphene modified straw material to process the method for black and odorous water: 将制备好的石墨烯秸秆材料浸泡在驯化好的污泥中搅拌，进行曝气处理，待载体表面生成污泥状的生物膜为止；The prepared graphene straw material is immersed in the domesticated sludge and stirred, and subjected to aeration treatment until a sludge-like biofilm is formed on the surface of the carrier; 在带有曝气装置的处理池中加入河道黑臭水，将黑臭水的pH调节至7.0，投加挂膜后的石墨烯改性秸秆材料，采用加热装置使处理池温度保持在25-30℃，通过曝气装置使DO保持在1.5～2.5mg/L之间，曝气处理72小时，出水COD降解率为85-95％，氨氮值为10-15mg/L。The black and odorous water from the river was added to the treatment tank with an aeration device, the pH of the black and odorous water was adjusted to 7.0, the graphene-modified straw material after filming was added, and a heating device was used to keep the temperature of the treatment tank at 25- At 30℃, the DO was kept between 1.5-2.5mg/L by the aeration device, and the aeration treatment was carried out for 72 hours. The COD degradation rate of the effluent was 85-95%, and the ammonia nitrogen value was 10-15mg/L. 2.根据权利要求1所述的使用新型石墨烯改性秸秆材料处理黑臭废水的方法，其特征在于：所述驯化好的污泥是将活性污泥用黑臭废水进行驯化处理，驯化方法为：污泥从污水处理厂取来后曝气8h，静置30min，捞出悬浮物质，排出上清液。将河道黑臭废水进行稀释，稀释倍数为20倍、15倍、10倍、5倍、2倍、不稀释；然后将最低浓度的黑臭废水加入活性污泥中，其体积比为2：1，曝气48h使污泥中DO始终保持在1.5～2.5mg/L之间，随后静置沉淀30min，排出上清液；然后逐步提高黑臭废水的浓度，重复上述过程，最后连续曝气24h后观察污泥活性恢复情况，至活性污泥呈黑褐色絮状，静沉时泥水分离迅速，污泥层密实，上清液清澈，驯化完成。2. the method for treating black and odorous wastewater using novel graphene-modified straw material according to claim 1, is characterized in that: the sludge that described domestication is good is that activated sludge is domesticated with black and odorous wastewater, and the domestication method For: after the sludge is taken from the sewage treatment plant, aeration is carried out for 8 hours, and it is allowed to stand for 30 minutes. The suspended substances are removed, and the supernatant is discharged. Dilute the black and odorous wastewater from the river, and the dilution ratio is 20 times, 15 times, 10 times, 5 times, 2 times, and undiluted; then add the black and odorous wastewater with the lowest concentration to the activated sludge, and its volume ratio is 2:1 , aeration for 48h to keep DO in the sludge between 1.5 and 2.5mg/L, then let it settle for 30min, and discharge the supernatant; then gradually increase the concentration of black and odorous wastewater, repeat the above process, and finally aeration continuously for 24h After observing the recovery of sludge activity, the activated sludge was black-brown flocculent, the mud and water were rapidly separated during the static settling, the sludge layer was dense, the supernatant was clear, and the domestication was completed. 3.根据权利要求1所述的使用新型石墨烯改性秸秆材料处理黑臭废水方法，其特征在于：投加挂膜后的石墨烯改性秸秆材料的比例为每立升黑臭水投加100-200块石墨烯改性秸秆材料。3. according to claim 1, use novel graphene-modified straw material to process black and odorous wastewater method, it is characterized in that: the ratio of the graphene-modified straw material after adding the hanging film is that every liter of black and odorous water is added 100-200 pieces of graphene modified straw material. 4.根据权利要求1所述的使用新型石墨烯改性秸秆材料处理黑臭废水方法，其特征在于：将使用后的石墨烯改性秸秆材料重新浸入驯化好的污泥中持续挂膜，又能够反复重新利用，直至载体材料破损。4. the method for treating black and odorous wastewater using novel graphene-modified straw material according to claim 1, is characterized in that: the graphene-modified straw material after use is re-immersed in the acclimated sludge and continues to hang film, and Can be reused repeatedly until the carrier material is damaged.
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