WO2021135906A1 - 一种针对黑臭地表水环境应急处理的复合材料及制备方法 - Google Patents

一种针对黑臭地表水环境应急处理的复合材料及制备方法 Download PDF

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WO2021135906A1
WO2021135906A1 PCT/CN2020/136104 CN2020136104W WO2021135906A1 WO 2021135906 A1 WO2021135906 A1 WO 2021135906A1 CN 2020136104 W CN2020136104 W CN 2020136104W WO 2021135906 A1 WO2021135906 A1 WO 2021135906A1
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water
composite material
preparation
activated carbon
black
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French (fr)
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缪恒锋
陈子文
姜莹莹
李雨平
阮文权
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Jiangnan 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/529—Processes or devices for preparing lime water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F2001/5218—Crystallization
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour

Definitions

  • the invention relates to a composite material for emergency treatment of black and smelly surface water environment and a preparation method thereof, and belongs to the field of environmental science and engineering technology.
  • flocculants such as iron or aluminum salts are usually added to quickly alleviate the black and odor phenomenon.
  • iron or aluminum salts are toxic to aquatic organisms and will affect subsequent water ecological restoration.
  • Activated carbon has the characteristics of high porosity and large specific surface area. It can adsorb most pollutants and has a good effect on decolorization and deodorization. On the one hand, activated carbon cannot increase dissolved oxygen in water. On the other hand, activated carbon is light in weight and is easily affected by water flow.
  • the use of pure materials or simply mixing in proportion can not fully exert its effect on the water environment.
  • the molecular level realizes the loading of nanometer calcium peroxide on the surface of activated carbon, improves the utilization efficiency of the material, reduces the dosage, and can reduce the risk of pH increase caused by excessive dosage.
  • the first object of the present invention is to provide a method for preparing a composite material for emergency treatment of black and odorous surface water environment, which specifically includes the following steps:
  • step (3) Centrifuging the suspension of step (2) to obtain a precipitate
  • step (3) Wash the precipitate of step (3) with distilled water until the final pH of the residual water reaches 8.4; then dry the obtained precipitate to obtain the composite material.
  • the activated carbon described in step (1) is after pretreatment.
  • the preparation method of pretreated activated carbon is: after soaking the activated carbon in 0.5-1.5 mol ⁇ L -1 hydrochloric acid for 1.5-2.5 hours, Rinse repeatedly with deionized water until it is neutral, then soak it with 0.5-1.5mol ⁇ L -1 sodium hydroxide for 1.5-2.5h, then rinse with deionized water until it is neutral, remove impurities, dry in 105°C oven, and grind After passing through a 200-mesh sieve.
  • the activated carbon described in step (1) is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the mass ratio of activated carbon, calcium chloride and water in step (1) is 1-3:13:30.
  • the mass-volume ratio of the activated carbon, ammonia water, and polyethylene glycol described in step (1) is (1-3) g: 15 mL: 120 mL.
  • the concentration of hydrogen peroxide in step (1) is 30%, and the dropping acceleration rate is 3 drops per minute.
  • the concentration of ammonia in step (1) is 1 mol ⁇ L -1.
  • the specific parameters for uniform stirring described in step (1) are set as: the stirring speed is 180 rpm, and the stirring time is 30 min.
  • the mass-volume ratio of activated carbon and hydrogen peroxide in step (1) is 1-3 g: 15 mL.
  • the reaction temperature in the entire reaction process of step (1) is room temperature (25°C).
  • the pH of the sodium hydroxide solution described in step (2) is 13.
  • the centrifugal separation parameters described in step (3) are set as follows: the centrifugal speed is 4000 rpm, and the centrifugal time is 10 min.
  • step (3) the solid after centrifugation is washed 3 times with NaOH solution.
  • the number of washing with distilled water in step (4) is 2 times
  • the drying described in step (4) is specifically drying in a vacuum oven at 80° C. for 2-4 hours.
  • the second object of the present invention is the composite material obtained by the preparation method of the present invention.
  • the third object of the present invention is the application of the composite material of the present invention in emergency treatment of black and smelly surface water environment.
  • the dosage of the composite material of the present invention in the black and smelly surface water is 150 mg/L.
  • the activated carbon-loaded calcium peroxide prepared by the present invention not only has the performance of activated carbon adsorption, but also has the performance of calcium peroxide to release oxygen and hydrogen peroxide, can improve the utilization rate of calcium peroxide, and is beneficial to ecological restoration of black and odorous water.
  • the activated carbon-loaded calcium peroxide prepared by the present invention is used in water treatment for the serious pollution of black and odorous water body, which can greatly improve the removal effect of pollutants, especially nitrogen, phosphorus and heavy metals, and can also increase the dissolved oxygen in the water body. And transparency, remove odorous substances, and will not harm the environment.
  • the composite material of the present invention treats a certain inferior grade V water, after 1 day, the ammonia nitrogen removal rate is 59%, the COD removal rate is 65%, the TP removal rate is 89%, and the water quality reaches the V grade water standard; Black and odorous water. After 3 days, the ammonia nitrogen removal rate is 58%, the COD removal rate is 63%, the TP removal rate is 87%, the dimethyl sulfide removal rate reaches 100%, the odor is significantly reduced, and the water DO reaches 3.12 mg/L, can eliminate black and odor.
  • FIG. 1 is an SEM image of the composite material of Example 1.
  • Fig. 2 is a characterization diagram of the NH 4 + -N change over time in the treatment of urban polluted water body by the composite material of the non-dosing and the dosing of the composite material of the embodiment 1 in the embodiment 2.
  • Fig. 3 is a characterization diagram of the COD change over time in the treatment of urban polluted water body by the composite material of the non-dosing and the dosing of the composite material of the embodiment 1 in the embodiment 2.
  • Fig. 4 is a characterization diagram of the total phosphorus TP in the treatment of urban polluted water body with time when the composite material of Example 2 is not added and the composite material of Example 1 is added.
  • Fig. 5 is a graph showing the change of the dissolved oxygen amount DO in the treatment of urban polluted water body with time when the composite material of Example 3 is not added and the composite material of Example 1 is added.
  • Fig. 6 is a characterization diagram of NH 4 + -N in the treatment of the overlying water of the black and smelly river with the composite material of the non-dosing and the dosing of the embodiment 1 in the embodiment 3 over time.
  • FIG. 7 is a characterization diagram of the COD change over time of the non-dosing and dosing of the composite material of Example 1 in the treatment of the overlying water of the black and smelly river with the non-dosing and dosing of the composite material in Example 3.
  • FIG. 7 is a characterization diagram of the COD change over time of the non-dosing and dosing of the composite material of Example 1 in the treatment of the overlying water of the black and smelly river with the non-dosing and dosing of the composite material in Example 3.
  • Fig. 8 is a graph showing the change over time of NH 4 + -N in the treatment of the overlying water of the black and smelly river with the composite material of the non-dosing and the dosing of the embodiment 1 in the embodiment 3.
  • Fig. 9 is a characterization diagram of the dimethyl sulfide in the treatment of the overlying water of the black and smelly river with the composite material of the non-dosing and the dosing of the embodiment 1 in the embodiment 3 over time.
  • Fig. 10 is the actual photographs of the black and smelly water before and after the treatment of the black and smelly river with the composite material of Example 1 without adding and adding the composite material of Example 1.
  • Figure 11 shows the changes of AVS in the bottom sludge in Example 4 throughout the experimental period.
  • Figure 12 shows the relative abundance of microorganisms at the genus level in the bottom sludge at the 0th, 28th and 61st days after being covered by the composite material in Example 4.
  • Fig. 13 shows the sequence number and diversity index of the 0th, 28th, and 61st days of sediment microorganisms after being covered by the composite material in Example 4.
  • Nessler's reagent spectrophotometry is used, specifically: (1) Drawing of standard curve: draw 0, 0.50, 1.00, 3.00, 5.00, 7.00 and 10.00mL ammonium standard use solution (0.1mg/ mL) in a 50mL colorimetric tube, add water to the mark, add 1.0mL potassium sodium tartrate solution (0.5kg/L), and mix well; add 1.5mL Nessler’s reagent and mix well.
  • COD test method use potassium dichromate method to determine, specifically: use a pipette to accurately draw 10 mL of oxidizing solution (0.01 mol/L) into a 250 mL triangular conical flask, add 5 mL of waste water sample to it, and cover with A small 50mL beaker, (one is to prevent floating matter from entering, and the other is to prevent evaporation during heating), put it into an oven that has been heated to 160°C, wait for the temperature to reach 160°C, count for 20 minutes, take it out, cool, and add 30mL to the bottle Distilled water, after cooling, add three drops of test ferrous iron indicator, and use standard ferrous ammonium sulfate solution (0.1mol/L) to drop to bright green to reddish brown as the end point; blank with double distilled water or water of the same purity instead The water sample is also dried for 20 minutes and then titrated with ferrous ammonium sulfate; it is calculated by substituting the formula: COD(
  • Test method for total phosphorus (TP) content use molybdenum antimony spectrophotometry after potassium persulfate digestion: (1) Drawing standard curve: draw 0, 0.50, 1.00, 3.00, 5.00, 7.00 and 10.00 mL phosphoric acid Salt standard use solution (2 ⁇ g/ml) in a 50ml colorimetric tube, add water to 25mL, add 4ml potassium persulfate solution (50g/L), digest at 121°C for 30min, cool down and dilute to 50mL, add 1mL 10% ascorbic acid solution, Mix well; after 30s, add 2mL molybdate solution and mix well.
  • TP total phosphorus
  • Atomic absorption spectroscopy is established based on the strong absorption of the element’s atomic resonance radiation by the ground state atoms of the element in the gaseous state.
  • the instrument used in the present invention is an AA-7000 atomic absorption spectrophotometer manufactured by Shimadzu Corporation. The working conditions of the instrument: wavelength 248.7nm, spectral bandwidth 0.4nm, lamp current is 6mA, acetylene flow rate is 1.5L/min, ratio of gas to supporting gas is 1:4, flame is oxidizing flame, background without neon lamp, water Measure directly after the sample has passed 0.45 ⁇ m.
  • Manganese content determination method Atomic absorption spectroscopy is established based on the strong absorption of the element’s atomic resonance radiation by the ground state atoms of the element in the gaseous state.
  • the instrument used in the present invention is an AA-7000 atomic absorption spectrophotometer manufactured by Shimadzu Co., Ltd. The working conditions of the instrument: wavelength 279.5nm, spectral bandwidth 0.4nm, lamp current is 6mA, acetylene flow rate is 1.5L/min, ratio of gas to supporting gas is 1:4, flame is oxidizing flame, using neon-free background, water Measure directly after the sample has passed 0.45 ⁇ m.
  • HS-SPME-GC-MS method Determination method of dimethyl sulfide: Before enrichment, the solid phase microextraction column (Supelco75 ⁇ m CAR/PDMS) is activated in the gas chromatograph inlet at 250°C for 30min in advance. . According to the SPME process, first add 5g of sodium chloride to a 40mL sample bottle, and then add 20mL of water sample. Keep the enrichment temperature at 50°C and rotate speed 500rpm for 30min. After the enrichment of the contaminated components was completed, the solid phase microextraction column was desorbed for 5 minutes in the inlet of a gas chromatograph operating in splitless mode at 250°C for analysis.
  • a gas chromatograph (Trace GC-MS, Thermo Fisher Scientific) equipped with a TG-WAXMS capillary column (Zebron, 30 m ⁇ 0.25 mm ID, 0.25 ⁇ m DF) and a quadrupole mass spectrometer (Trace GC-MS, Thermo Fisher Scientific) was used for detection of the compounds.
  • the temperature program is set to: initial temperature and held 40 °C 2min, raised to 8 °C ⁇ min -1 to 220 deg.] C and held 3min, finally 8 °C ⁇ min -1 was raised to 250 deg.] C and held after the end of the analysis 3min.
  • the carrier gas uses helium with a constant flow rate of 0.5 mL ⁇ min -1 .
  • the temperature of the ion source and the transmission line are both 250°C, operating in the mass range of 40-300amu in the full scan mode, and the IE energy is 70eV.
  • a preparation method of composite material for emergency treatment of black and smelly surface water environment specifically including the following steps:
  • the solution contains a certain amount of ammonia, which can neutralize hydrogen chloride to generate ammonium chloride and promote the generation of calcium peroxide, that is, the reaction 2HCl+2NH 3 ⁇ 2NH 4 Cl;
  • the added solution of hydrogen peroxide slowly turns from black to gray, and at this time, the calcium peroxide composite material solution is obtained, and the whole preparation process is completed at room temperature;
  • the calcium peroxide composite material solution in step (2) is added to the sodium hydroxide solution with pH 13 to form an alkaline medium until the pH value reaches 11.5, and the mixture becomes a gray suspension;
  • the gray precipitate was obtained by centrifugation, and during the centrifugation process, the solid after centrifugation was washed with NaOH solution 3 times; finally, washed with distilled water twice until the final pH of the residual water reached 8.4; the resulting precipitate was heated at 80°C After drying in a vacuum oven, the composite material can be obtained.
  • the specific morphology is shown in Figure 1.
  • Figure 1 is an SEM image of the composite material prepared in Example 1. It can be seen from the figure that calcium peroxide is successfully loaded on the surface of activated carbon.
  • the composite material of Example 1 is used for the treatment of urban polluted water bodies (the dosage of composite material is 150 mg/L), and the specific steps are as follows:
  • Example 2 Take 150 mg of the composite material of Example 1 and add 5 mL of deionized water to moisten it into a slurry, add it to 1L of urban polluted water, stir it evenly, and measure the concentrations of ammonia nitrogen, TP and COD at 4, 12, and 24 hours, respectively.
  • Figure 2- Figure 5 and Table 1 show the various performance changes in the treatment of urban polluted water bodies with the composite material of the non-dosing and the dosing of Example 1. From Figure 2 to Figure 5 and Table 1, it can be seen that the main pollution indicators (ammonia nitrogen, COD and total phosphorus) concentration in the river show a downward trend. After 24 hours, the removal rate of ammonia nitrogen, COD and total phosphorus reached 59%. 65% and 89%, reflecting the good emergency treatment effect for river pollutant indicators.
  • the main pollution indicators ammonia nitrogen, COD and total phosphorus
  • Example 1 The composite material of Example 1 is used for the treatment of overlying water on a black and smelly river (the dosage of composite material is 150 mg/L), and the specific steps are as follows:
  • Figures 6, 7, 8, 9 and Table 2 show that the concentrations of ammonia nitrogen, COD, total phosphorus and dimethyl sulfide all show a downward trend.
  • the iron and manganese ion concentrations in the black and odorous water are respectively 0.313mg/L and 0.421mg/L can catalyze the hydrogen peroxide generated by calcium peroxide to generate hydroxyl radicals, oxidize organic pollutants and some odorous substances.
  • the activated carbon in the composite material can absorb organic pollutants and odorous substances.
  • the Ca(OH) 2 produced by the reaction has a flocculating effect.
  • the calcium ions dissolved in the water can combine with the phosphate ions in the water to form hydroxyapatite; the final removal rates of ammonia nitrogen, COD, total phosphorus and dimethyl sulfide are respectively They are 58%, 63%, 87% and 100%.
  • the dissolved oxygen concentration in the black and odorous water is kept above 3mg ⁇ L -1 ( Figure 5), and the upper layer of the black and odorous water with the composite material becomes clear and transparent after 3 days ( Figure 10).
  • Example 1 has a good effect on the emergency treatment of urban black and smelly rivers. First, it can quickly increase the dissolved oxygen in the water body and eliminate the peculiar smell (dimethyl sulfide) of the water body; secondly, it can gradually improve the water habitat and improve transparency. Reduce ammonia nitrogen and other toxic substances; finally, it can greatly reduce water pollution indicators (COD, total phosphorus, etc.).
  • Example 1 The composite material of Example 1 is used for the repair of river bottom mud (according to the 0.24kg ⁇ m -2 dosage, the composite material is evenly spread on the surface of the heavily polluted river, and allowed to settle to the bottom of the river for coverage of the bottom mud) ,Specific steps are as follows:
  • a Duantou Bang (N31°33'20.08”, E120°16'36.52”) in Wuxi City, with a length of about 0.32km, an average width of about 12m, a water depth of about 2 to 2.5m, and a bottom mud thickness of about 0.75m; Adding amount of 0.24kg ⁇ m -2
  • the composite material will be evenly spread on the surface of the heavily polluted river after being wetted with water, and allowed to settle to the bottom of the river for sediment cover; a total of 6 in the river (every 50m) Sampling points, and the 6 sampling points are regarded as parallel control monitoring points.
  • a water collector and a grab-type gravity sampler are used to collect the overlying water and surface sediment (0-10cm deep) at 6 sampling points respectively, and the interstitial water is obtained by centrifuging the sediment in a low-temperature centrifuge.
  • One month before the experiment (August 2019 to September 2019) as a reference, water samples and sediment were collected every 7 days for index determination. After the composite material was added, water samples and sediment were collected for index determination. The period is 2 months (September 2019-November 2019).
  • Figure 11 shows the changes of AVS in the sediment during the whole experiment period. It can be seen from Figure 11 that the average content of AVS in the sediment before the experiment is 8.52 mg ⁇ g -1 , and after the composite material is covered, the AVS in the sediment shows a downward trend. At the 28th day, the AVS removal rate reached the maximum value of 44.81%, and the AVS removal rate was 37.08% at the end of the experiment.
  • Figure 12 shows the relative abundance of microorganisms at the genus level in the bottom sludge at the 0th, 28th, and 61st days after being covered by the composite material. It can be seen from Figure 12 that before the composite material is covered, the main bacterial genera in the bottom mud are norank_f__Bacteroidetes_vadinHA17 (15.26%), norank_f__Anaerolineaceae (4.76%), Caldisericum (4.65%), Lactivibrio (4.37%), Romboutsia (2.08%) and Syntrophorhabdus (1.83%).
  • norank_f__Anaerolineaceae belongs to the genus of anaerobic bacteria, which will decompose nitrogenous organic matter under anaerobic conditions, thereby increasing the concentration of NH 4 + -N in water bodies; Caldisericum can reduce sulfate to H 2 S under anaerobic conditions and release it from the bottom sludge It will cause the suspended matter on the surface of the sediment to enter the overlying water again and affect the transparency of the water body.
  • Romboutsia and Syntrophorhabdus are the main bacteria in the anaerobic acid production [101] , which will cause the anaerobic acidification of the sediment to be covered by the composite material.
  • the relative abundance of bacteria decreased significantly, dropping to 1.35%, 0.3%, 0.1%, and 0.23% on the 28th day, and 2.22%, 1.96%, 1.43%, and 1.1% on the 61st day. It shows that composite material covering can significantly reduce the relative abundance of anaerobic bacteria in the bottom sludge, reduce the risk of NH 4 + -N and H 2 S release, and prevent the acidification of the bottom sludge.
  • Table 3 shows the number of microbial sequence and diversity index in the 0th, 28th and 61st days of the sediment covered by the composite material. It can be seen from Table 3 that the number of valid sequences ranges from 41019 to 44809, and the coverage of samples is greater than 99%, indicating that the results of microbial sequencing can express the diversity of microorganisms in the bottom mud.
  • Chao and ACE indices can reflect the abundance of microbial communities.
  • the Chao and ACE indices in each sample are 802-868 and 792-861, respectively, which proves that the abundance of microbial communities in the sediments is similar.
  • Shannon index and Simpson index directly reflect the diversity of species. The higher the Shannon index and the lower the Simpson index, the better the community diversity. It can be seen from Table 3 that compared with before the experiment, the Shannon index increased and the Simpson index decreased after the composite material covering, indicating that the composite material covering can enrich the diversity of the microbial community in the sediment.
  • Figure 13 shows the changes in the proportions of different phosphorus forms in sediments during the experimental period. It can be seen from Figure 13 that before the experiment, NH 4 Cl-P (21% ⁇ 24%), Fe/Al-P (13% ⁇ 19%), Ca-P (11% ⁇ 13%) in the bottom sludge It is very close to Res-P (47% ⁇ 51%), and Res-P accounts for the main part. After adding composite materials, the proportions of NH 4 Cl-P and Res-P both showed a downward trend, while the proportions of Fe/Al-P and Ca-P increased significantly. At the 21st day, the proportions of Fe/Al-P and The maximum proportion of Ca-P is 28% and 40%, respectively. After a large amount of organic phosphorus in Res-P is mineralized, it is converted into Fe/Al-P and Ca-P.
  • the composite material has good stability in the repair of bottom mud and is not affected by the entry of external pollutants.
  • Adjust the adding time of pretreated activated carbon add it after the calcium peroxide solution is formed, the specific preparation method is as follows:
  • the granular activated carbon purchased from Sinopharm Chemical Reagent Co., Ltd. was soaked in 1mol ⁇ L -1 hydrochloric acid for 2 hours, then washed repeatedly with deionized water to neutrality, and then soaked in 1mol ⁇ L -1 sodium hydroxide for 2 hours. Rinse with deionized water repeatedly until it is neutral, remove impurities, dry in an oven at 105°C, and pass through a 200-mesh sieve after grinding.
  • the gray precipitate was separated by centrifugation, and during the centrifugation, the solid after centrifugation was washed 3 times with NaOH solution. Finally, it is washed twice with distilled water until the final pH of the residual water reaches 8.4; the obtained precipitate is dried in a vacuum oven at 80° C. to obtain a composite material.
  • Table 5 shows the test results of the treatment of urban polluted water bodies:
  • Table 6 shows the test results of the treatment of the overlying water on the black and smelly river:
  • Example 1 DO concentration in Example 1 is 3.12 mg/L, which is much greater than that in Comparative Examples 1 and 2, and the removal rate of ammonia nitrogen, COD, TP, iron and manganese is also much higher.
  • Comparative Examples 1 and 2 while the pH value in Example 1 was only slightly higher than that in Comparative Examples 1 and 2.
  • Comparative Example 2 both Example 1 and Comparative Example 2 were lower than the detection line, while the comparative example 1
  • the concentration at the end of the experiment is 44 ⁇ g/L, which further shows that the preparation method of Example 1 is better than that of Comparative Example 2 and Comparative Example 1, and that the preparation method of Example 1 is the best.

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Abstract

一种针对黑臭地表水环境应急处理的复合材料及制备方法，具体包括以下步骤：(1)将活性炭和氯化钙、氨水、聚乙二醇和水置于搅拌器中搅拌均匀，之后再滴加过氧化氢，滴加结束之后，得到过氧化钙复合材料溶液；(2)在步骤(1)得到的过氧化钙复合材料溶液加入氢氧化钠溶液，直到pH值达到11.5，得到悬浮液；(3)将步骤(2)的悬浊液通过离心分离得到固体；(4)用蒸馏水洗涤步骤(3)的固体，直到残留水的最终pH达到8.4；将所得沉淀物烘干，即得到所述的复合材料。

Description

一种针对黑臭地表水环境应急处理的复合材料及制备方法 技术领域
本发明涉及一种针对黑臭地表水环境应急处理的复合材料及制备方法，属于环境科学与工程技术领域。
背景技术
随着经济的发展，水污染问题日益加重，水体富营养化甚至出现黑臭河道。至2017年2月，中国共有1861个水体(85.7％的河流和14.3％的湖泊)被标记为黑臭水。为此，2018年9月30日住房和城乡建设部与生态环境部联合发布了《城市黑臭水体治理攻坚战实施方案》，明确要求：至2020年底，各省、自治区地级及以上城市建成区黑臭水体消除比例高于90％。因此，如何处理黑臭水体是亟需解决的问题。
当水体变成黑臭时，会丧失了水体自净功能，由于水体透明度低，污染物质多，不利于沉水植物生长，而人工曝气联合生物修复时间跨度长，见效慢。
目前为了提高水体透明度，通常投加铁盐或铝盐等絮凝剂来快速缓解黑臭现象，但铁盐或铝盐对水生生物有毒，会影响后续水生态修复。活性炭具有孔隙率高、比表面积大等特点，可以吸附大部分污染物，对脱色除臭均有良好效果，但是一方面活性炭不能增加水体溶解氧，另一方面活性炭质轻，易受水流影响。
发明内容
为了解决上述至少一个问题，针对目前对于过氧化钙的制备和在地表水环境中的应用，均是纯材料使用或者简单按比例混合，无法完全发挥其对于水环境的作用的情况，本发明从分子层面实现纳米过氧化钙在活性炭表面的负载，提高材料的利用效率，减少投加量，并且可以降低过量投加导致的pH升高风险。
本发明的第一个目的是提供一种针对黑臭地表水环境应急处理的复合材料的制备方法，具体包括以下步骤：
(1)将活性炭、氯化钙、氨水、聚乙二醇和水置于搅拌器中搅拌均匀，之后再滴加过氧化氢，滴加过程中继续搅拌，滴加结束之后，得到过氧化钙复合材料溶液；
(2)在步骤(1)得到的过氧化钙复合材料溶液加入氢氧化钠溶液，直到pH值达到11.5，得到悬浊液；
(3)将步骤(2)的悬浊液通过离心分离得到沉淀物；
(4)用蒸馏水洗涤步骤(3)的沉淀物，直到残留水的最终pH达到8.4；然后将所得 沉淀物烘干，即得到所述的复合材料。
在一种实施方式中，步骤(1)所述的活性炭为预处理之后的，预处理活性炭的制备方法为：将活性炭使用0.5-1.5mol·L -1的盐酸浸泡1.5-2.5h后，用去离子水反复冲洗至中性，再用0.5-1.5mol·L -1氢氧化钠浸泡1.5-2.5h后，用去离子水反复冲洗至中性，去除杂质后，105℃烘箱烘干，研磨后过200目筛。
在一种实施方式中，步骤(1)所述的活性炭购自国药集团化学试剂有限公司。
在一种实施方式中，步骤(1)所述的活性炭、氯化钙和水的质量比为1-3：13：30。
在一种实施方式中，步骤(1)所述的活性炭、氨水、聚乙二醇的质量体积比为(1-3)g：15mL：120mL。
在一种实施方式中，步骤(1)所述的过氧化氢的浓度为30％，滴加速率为每分钟3滴。
在一种实施方式中，步骤(1)所述的氨水的浓度为1mol·L -1。
在一种实施方式中，步骤(1)所述的搅拌均匀的具体参数设置为：搅拌速度为180rpm，搅拌时间为30min。
在一种实施方式中，步骤(1)中活性炭和过氧化氢的质量体积比为1-3g：15mL。
在一种实施方式中，步骤(1)整个反应过程中的反应温度为室温(25℃)。
在一种实施方式中，步骤(2)所述的氢氧化钠溶液的pH为13。
在一种实施方式中，步骤(3)所述的离心分离的参数设置为：离心速度为4000rpm，离心时间为10min。
在一种实施方式中，步骤(3)中先将离心后固体用NaOH溶液洗涤3次。
在一种实施方式中，步骤(4)所述的用蒸馏水洗涤次数为2次，
在一种实施方式中，步骤(4)所述的烘干具体为80℃真空烘箱烘干2-4h。
本发明的第二个目的是本发明的制备方法得到的复合材料。
本发明的第三个目的是本发明的复合材料在黑臭地表水环境应急处理中的应用。
在一种实施方式中，本发明的复合材料在黑臭地表水中的投加量为150mg/L。
本发明的有益效果：
(1)本发明制备的活性炭负载过氧化钙既具备活性炭吸附的性能，又具备过氧化钙释放氧气和过氧化氢的性能，能够提高过氧化钙的利用率，有利于黑臭水体生态修复。
(2)本发明制备的活性炭负载过氧化钙针对黑臭水体污染严重的特点，用于水处理，能够很大程度提高污染物的去除效果，尤其是氮磷、重金属，也能提高水体溶解氧和透明度，去除臭味物质，不会危害环境。
(3)本发明的复合材料处理某一劣Ⅴ类水，1天后，氨氮去除率为59％，COD去除率为65％，TP去除率为89％，水质达到Ⅴ类水标准；处理某一黑臭类水，3天后，氨氮去除率为58％，COD去除率为63％，TP去除率为87％，二甲基硫醚的去除率达到100％，臭味明显降低，水体DO达到3.12mg/L，可消除黑臭。
附图说明
图1为实施例1的复合材料的SEM图。
图2为实施例2中未投加和投加实施例1的复合材料对于城市污染水体处理中的NH 4 +-N随时间变化表征图。
图3为实施例2中未投加和投加实施例1的复合材料对于城市污染水体处理中的COD随时间变化表征图。
图4为实施例2中未投加和投加实施例1的复合材料对于城市污染水体处理中的总磷TP随时间变化表征图。
图5为实施例3中未投加和投加实施例1的复合材料对于城市污染水体处理中的溶氧量DO随时间变化表征图。
图6为实施例3中未投加和投加实施例1的复合材料对于黑臭河道上覆水处理中的NH 4 +-N随时间变化表征图。
图7为实施例3中未投加和投加实施例1的复合材料对于黑臭河道上覆水处理中的未投加和投加复合材料COD随时间变化表征图。
图8为实施例3中未投加和投加实施例1的复合材料对于黑臭河道上覆水处理中的NH 4 +-N随时间变化表征图。
图9为实施例3中未投加和投加实施例1的复合材料对于黑臭河道上覆水处理中的二甲基硫醚随时间变化表征图。
图10为实施例3中未投加和投加实施例1的复合材料对于黑臭河道上覆水处理前后黑臭水体的实际拍摄照片。
图11为实施例4中底泥AVS在整个实验期的变化。
图12为实施例4中复合材料覆盖后第0、28和61d底泥中微生物在属水平上的相对丰度。
图13为实施例4中复合材料覆盖后第0、28和61d底泥微生物序列数和多样性指数。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用 于限制本发明。
测试方法：
1、氨氮含量的测试方法：采用纳氏试剂分光光度法，具体为：(1)标准曲线的绘制：吸取0、0.50、1.00、3.00、5.00、7.00和10.00mL铵标准使用液(0.1mg/mL)于50mL比色管中，加水至标线，加1.0mL酒石酸钾钠溶液(0.5kg/L)，混匀；加1.5mL纳氏试剂，混匀。放置10min后，在波长420nm处，用光程10mm比色皿，以0浓度为参比，测量吸光度；然后绘制标准曲线；(2)水样测定：取适量的水样于50mL比色管中，稀释至标线，加1.0mL酒石酸钾钠溶液，混匀；加1.5mL纳氏试剂，混匀；显色10min后，在420nm处用紫外分光光度计(TU1810，北京普析，中国)测量吸光度；(3)计算：氨氮(mg/L)＝1000×m/V；式中：m为由吸光度查得的氨氮量(mg)；V为水样体积(mL)。
2、COD的测试方法：采用重铬酸钾法测定，具体为：用移液管准确吸取10mL氧化液(0.01mol/L)于250mL三角锥瓶中，吸取废水样5mL加入其中，上盖以50mL小烧杯，(一是防止漂浮物进入，二是防止加热时蒸发)，放入已升温至160℃的烘箱中，等温度热至160℃时，计时20min，取出、冷却，瓶内加入30mL蒸馏水，待冷却后，加入三滴试亚铁灵指示剂，用标准硫酸亚铁铵溶液(0.1mol/L)滴至亮绿色变红褐色为终点；空白用二次蒸馏水或同等纯度的水代替水样，同样烘20min后用硫酸亚铁铵滴定后；代入公式计算得出：COD(mol/L)＝(V 0-V 1)×C×8×1000/V；其中：V 0：空白滴定时消耗硫酸亚铁铵毫升数；V 1：为水样滴定时消耗硫酸亚铁铵毫升数；C：为硫酸亚铁铵溶液摩尔浓度mol/L；8：(1/4)O 2的摩尔质量以mol/L为单位的换算值。
3、总磷(TP)含量的测试方法(过硫酸钾消解后用钼锑抗分光光度法)：(1)标准曲线的绘制：吸取0、0.50、1.00、3.00、5.00、7.00和10.00mL磷酸盐标准使用液(2μg/ml)于50ml比色管中，加水至25mL，加入4ml过硫酸钾溶液(50g/L)，121℃消解30min，冷却后定容至50mL，加入1mL10％抗坏血酸溶液，混匀；30s后加2mL钼酸盐溶液充分混匀，显色15min后，在700nm处用紫外分光光度计(TU1810，北京普析，中国)测量吸光度；然后绘制标准曲线。(2)水样测定：取适量的水样于50mL比色管中，定容至25mL标线，加4.0mL过硫酸钾钠溶液后，在121℃消解30min，冷却后定容至50mL，加入1mL10％抗坏血酸溶液，混匀；30s后加2mL钼酸盐溶液充分混匀，显色15min后，在700nm处用紫外分光光度计(TU1810，北京普析，中国)测量吸光度。(3)计算：总磷(mg/L)＝m/V；式中：m为由校准曲线查得的磷量(μg)；V为水样体积(mL)。
4、铁含量测定方法(原子吸收光谱法)：原子吸收光谱法是依据处于气态的被测元素基态原子对该元素的原子共振辐射有强烈的吸收作用而建立的。本发明使用的仪器是岛津有限 公司的AA-7000原子吸收分光光度计。仪器的工作条件：波长248.7nm，光谱带宽0.4nm，灯电流为6mA，乙炔流量为1.5L/min，燃气与助燃气比为1:4，火焰为氧化性火焰，采用无氖灯背景，水样过0.45μm后直接测定。
5、锰含量测定方法(原子吸收光谱法)：原子吸收光谱法是依据处于气态的被测元素基态原子对该元素的原子共振辐射有强烈的吸收作用而建立的。本发明使用的仪器是岛津有限公司的AA-7000原子吸收分光光度计。仪器的工作条件：波长279.5nm，光谱带宽0.4nm，灯电流为6mA，乙炔流量为1.5L/min，燃气与助燃气比为1:4，火焰为氧化性火焰，采用无氖灯背景，水样过0.45μm后直接测定。
6、二甲基硫醚的测定方法(HS-SPME-GC-MS法)：富集前预先将固相微萃取柱(Supelco75μm CAR/PDMS)在气相色谱仪进样口于250℃下活化30min。按照SPME流程，先在容量为40mL的样品瓶中加入5g氯化钠，然后加入20mL水样，保持富集温度50℃、转速500rpm富集30min。完成污染组分的富集后，在250℃下以不分流模式操作的气相色谱仪进样口中将固相微萃取柱解吸5min进行分析。使用配备有TG-WAXMS毛细管柱(Zebron，30m×0.25mm ID，0.25μm DF)、带有四极杆质谱的气相色谱仪(Trace GC-MS，Thermo Fisher Scientific)进行化合物的检测。升温程序设置为：初始温度40℃并保持2min，以8℃·min -1升高至220℃并保持3min，最后以8℃·min -1升至250℃并保持3min后结束分析。载气使用氦气，恒定流量0.5mL·min -1。离子源和传输线的温度均为250℃，在全扫描模式下在40-300amu的质量范围进行内操作，IE能量为70eV。
实施例1
一种针对黑臭地表水环境应急处理的复合材料的制备方法，具体包括以下步骤：
(1)将购自国药集团化学试剂有限公司的颗粒活性炭使用1mol·L -1的盐酸浸泡2h后，用去离子水反复冲洗至中性，再用1mol·L -1氢氧化钠浸泡2h后，用去离子水反复冲洗至中性，去除杂质后，105℃烘箱烘干，研磨后过200目筛，得到预处理的活性炭。
(2)取30mL去离子水于500mL烧杯中，先后加入2g步骤(1)的预处理粉末活性炭，13g氯化钙，15mL含量为1mol·L -1的氨水溶液，120mL PEG 200(聚乙二醇)，搅拌均匀后放置于磁力搅拌器并保持恒定转速(180rpm)搅拌30分钟后；再以每分钟3滴的速率加入15mL的30％过氧化氢到体系中，此时溶液中发生反应CaCl 2+H 2O 2→CaO 2+2HCl；溶液中含有一定量的氨水，其能中和氯化氢生成氯化铵，促进过氧化钙的生成，即反应2HCl+2NH 3→2NH 4Cl；随着过氧化氢的加入溶液由黑色缓慢变成灰色，此时就得到了过氧化钙复合材料溶液，整个制取过程在室温条件下完成；
(3)反应结束，在步骤(2)的过氧化钙复合材料溶液加入pH为13的氢氧化钠溶液以形成碱性介质，直到pH值达到11.5，混合物变为灰色悬浮液；将悬浊液通过离心分离得到灰色沉淀物，并且在离心过程之中，将离心后固体用NaOH溶液洗涤3次；最后用蒸馏水再洗涤两次，直到残留水的最终pH达到8.4；将所得沉淀物在80℃真空烘箱烘干，即可以得到复合材料，具体形貌如图1所示。
图1为实施例1制备得到的复合材料SEM图，从图中可以看出：过氧化钙成功负载在活性炭表面上。
实施例2
将实施例1的复合材料用于城市污染水体的处理(复合材料投加量为150mg/L)，具体步骤如下：
取实施例1的复合材料150mg加入5mL去离子水润湿成浆液，投加到1L城市污染水中，搅拌均匀，分别在4、12、24h时测定氨氮、TP和COD浓度。
图2-图5、表1为未投加和投加实施例1的复合材料对于城市污染水体处理中的各种性能变化。从图2-图5和表1可以看出：河道主要的污染指标(氨氮、COD和总磷)浓度均呈现下降的趋势，24h后氨氮、COD和总磷的去处率分别达到了59％、65％和89％，体现了针对河道污染物指标体现了良好的应急处理效果。
表1 未投加和投加复合材料实验前后水质结果
例 氨氮(mg/L) COD(mg/L) 总磷(mg/L)
原水 4.71 43 1.21
实施例2 1.46 16 0.13
去除率 69％ 63％ 89％
实施例3：
将实施例1的复合材料用于黑臭河道上覆水的处理(复合材料投加量为150mg/L)，具体步骤如下：
用50L桶收集某一黑臭河道上覆水，取实施例1的复合材料7.5g加入250mL去离子水润湿成浆液，投加到50L黑臭水中，搅拌均匀(复合填料的投加量为150mg/L)。
通过3天实验，图6、7、8、9和表2表明：氨氮、COD、总磷和二甲基硫醚浓度均呈现下降的趋势，这是因为黑臭水体中铁、锰离子浓度分别为0.313mg/L和0.421mg/L可以催化过氧化钙生成的过氧化氢，生成羟基自由基，氧化有机污染物质和部分臭味物质，复合材料中的活性炭可以吸附有机污染物质和臭味物质，反应生成的Ca(OH) 2具有絮凝的作用，溶于水中的钙离子可以与水中的磷酸根离子结合生成羟基磷灰石；最终氨氮、COD、总磷和二甲 基硫醚的去除率分别为58％、63％、87％和100％。黑臭水体中溶解氧浓度保持在3mg·L -1以上(图5)，投加复合材料的黑臭水体上层水3天后变得清澈透明(图10)。
结果表明，实施例1的复合材料对城市黑臭河道应急处理具有良好的效果，首先能够迅速提升水体溶解氧，消除水体异味(二甲基硫醚)；其次能够逐步提升水体生境，提升透明度，降低氨氮等毒性物质；最后能大幅降低水体污染指标(COD、总磷等)。
表2 未投加和投加复合材料实验前后水质理化指标
Figure PCTCN2020136104-appb-000001
实施例4
将实施例1的复合材料用于河道底泥的修复(按照0.24kg·m -2投加量将复合材料均匀铺洒在重污染河道表面，并让其沉降至河底用于底泥覆盖)，具体步骤如下：
无锡市某断头浜(N31°33'20.08”，E120°16'36.52”)，长约0.32km，平均宽度约为12m，水深约为2～2.5m，底泥厚度约为0.75m；按照0.24kg·m -2投加量将复合材料加水润湿后均匀铺洒在重污染河道表面，并让其沉降至河底用于底泥覆盖；在该河道(每隔50m)共设置6个采样点，并将该6个采样点视为平行控制监测点位。
利用采水器和抓斗式重力采样器分别收集6个采样点上覆水和表层底泥(0～10cm深)，通过低温离心机离心底泥获得间隙水。在实验前1个月(2019年8月～2019年9月)作为参照，约隔7d采集水样和底泥进行指标测定，复合材料投加后，采集水样和底泥进行指标测定，实验周期为2个月(2019年9月～2019年11月)。
测试结果如图11-图13、表3、表4所示。
图11是底泥AVS在整个实验期的变化，从图11可以看出：底泥中AVS在实验前的含量均值为8.52mg·g -1，复合材料覆盖后，底泥AVS呈现下降趋势，在第28d时AVS去除率达到最大值为44.81％，实验结束时AVS去除率是37.08％。
图12为复合材料覆盖后第0、28和61d底泥中微生物在属水平上的相对丰度。从图12可以看出：在复合材料覆盖前，底泥中主要菌属为norank_f__Bacteroidetes_vadinHA17(15.26％)、norank_f__Anaerolineaceae(4.76％)、Caldisericum(4.65％)、Lactivibrio(4.37％)、Romboutsia(2.08％)和Syntrophorhabdus(1.83％)。其中norank_f__Anaerolineaceae属于厌氧菌属，在厌氧条件下会分解含氮有机物，进而增加水体NH 4 +-N浓度；Caldisericum在厌氧条件下可将硫酸盐还原为H 2S，从底泥中释放出来，会导致底泥表面易悬浮物质再次进入上 覆水影响水体透明度，而Romboutsia和Syntrophorhabdus均是在厌氧产酸中的主要菌属 [101]，会导致底泥酸化复合材料覆盖后，厌氧菌相对丰度明显下降，第28d分别降至1.35％、0.3％、0.1％和0.23％；在第61d变为2.22％、1.96％、1.43％和1.1％。表明复合材料覆盖可以明显降低底泥中厌氧菌群的相对丰度，减小NH 4 +-N和H 2S释放的风险，防止底泥酸化。
表3为复合材料覆盖后第0、28和61d底泥微生物序列数和多样性指数。从表3可以看出：有效序列数量范围41019～44809，样品的覆盖率大于99％，表明微生物测序的结果可以表达底泥中微生物的多样性。Chao和ACE指数能够反应微生物群落的丰富度，各样品中Chao和ACE指数分别为802～868和792～861，证明底泥中微生物群落的丰度相似。Shannon指数和Simpson指数直接反应出物种的多样性，Shannon指数越高且Simpson指数越低，群落多样性越好。由表3可知，与实验前相比，复合材料覆盖后，Shannon指数升高，Simpson指数降低，说明复合材料覆盖可丰富底泥中微生物群落的多样性。
表3 底泥中微生物样本多样性指数
Figure PCTCN2020136104-appb-000002
从表4可以看出：在复合材料覆盖后导致底泥Tot-P前期含量出现升高的现象(表4)，此现象进一步证实了间隙水DIP被固定在底泥中，减小了底泥磷释放的风险。
表4 底泥Tot-P变化
Figure PCTCN2020136104-appb-000003
图13为底泥不同磷形态在实验周期所占比例的变化。从图13可以看出：在实验前，底泥中NH 4Cl-P(21％～24％)、Fe/Al-P(13％～19％)、Ca-P(11％～13％)和Res-P(47％～51％) 所占比例均很接近，其中Res-P占主要部分。投加复合材料后，NH 4Cl-P和Res-P所占比例均呈现下降趋势，而Fe/Al-P和Ca-P所占比例明显上升，在第21d时，Fe/Al-P和Ca-P占比达到最大分别为28％和40％，Res-P中大量的有机磷被矿化后，转化为Fe/Al-P和Ca-P。
结合图11-图13、表3、表4所示，复合材料对底泥的修复具有良好的稳定性，不受外源污染物进入的影响。
对照例1
将实施例1中复合材料的制备方法中的“滴加过氧化氢”换为“一次性加入15mL的30％过氧化氢”，其他参数保持不变，得到复合材料。
对照例2
调整预处理活性炭的加入时间：在过氧化钙溶液形成之后加入，具体制备方法如下：
将购自国药集团化学试剂有限公司的颗粒活性炭，使用1mol·L -1的盐酸浸泡2h后，用去离子水反复冲洗至中性，再用1mol·L -1氢氧化钠浸泡2h后，用去离子水反复冲洗至中性，去除杂质后，105℃烘箱烘干，研磨后过200目筛。取30mL去离子水于500mL烧杯中，先后加入13g氯化钙，15mL含量为1mol·L -1的氨水溶液，120mLPEG 200(聚乙二醇)，搅拌均匀后放置于磁力搅拌器并保持恒定转速(180rpm)搅拌。再以每分钟3滴的速率加入15mL的30％过氧化氢到体系中，此时溶液中发生反应CaCl 2+H 2O 2→CaO 2+2HCl；溶液中含有一定量的氨水，其能中和氯化氢生成氯化铵，促进过氧化钙的生成，即反应2HCl+2NH 3→2NH 4Cl；随着过氧化氢的加入溶液由无色缓慢变成淡黄色，此时就得到了过氧化钙溶液，然后加入2g预处理粉末活性炭，继续在磁力搅拌器并保持恒定转速(180rpm)搅拌30分钟，整个制取过程在室温条件下完成。结束后，加入pH为13的氢氧化钠溶液以形成碱性介质，直到pH值达到11.5，混合物变为灰色悬浮液。通过离心分离灰色沉淀物，并且在离心过程之中，将离心后固体用NaOH溶液洗涤3次。最后，用蒸馏水再洗涤两次，直到残留水的最终pH达到8.4；将所得沉淀物在80℃真空烘箱烘干，得到复合材料。
将对照例1和2的复合材料按照实施例2、3的方式进行性能测试，测试结果如下表5、表6所示：
表5为城市污染水体的处理的测试结果：
表5 未投加和投加复合材料实验前后水质结果
  氨氮(mg/L) COD(mg/L) 总磷(mg/L)
原水 4.71 43 1.21
对照例1 3.46 34 0.58
对照例1的去除率 26％ 21％ 52％
对照例2 2.15 23 0.2
对照例2的去除率 54％ 47％ 83％
结合表1，对于氨氮、COD和TP去除效果，实施例2＞对照例2＞对照例1，这表明实施例1制备方法要优于对照例2和对照例1，实施例1制备方法最好。
表6为黑臭河道上覆水的处理的测试结果：
表6 未投加和投加复合材料实验前后水质理化指标
Figure PCTCN2020136104-appb-000004
从表6可以看出，在实验结束时，实施例1中DO浓度为3.12mg/L，远远大于对照例1和2，而氨氮、COD、TP、铁和锰的去除率也远远高于对照例1和2，同时实施例1中pH值仅仅略高于对照例1和2，对于嗅味物质二甲基硫醚，实施例1和对照例2均低于检测线，而对照例1在实验结束时浓度为44μg/L，这也进一步说明实施例1制备方法要优于对照例2和对照例1，实施例1制备方法最好。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (14)

  1. 一种针对黑臭地表水环境应急处理的复合材料的制备方法，其特征在于，具体包括以下步骤：
    (1)将活性炭、氯化钙、氨水、聚乙二醇和水置于搅拌器中搅拌均匀，之后再滴加过氧化氢，滴加过程中继续搅拌，滴加结束之后，得到过氧化钙复合材料溶液；
    (2)在步骤(1)得到的过氧化钙复合材料溶液加入氢氧化钠溶液，直到pH值达到11.5，得到悬浊液；
    (3)将步骤(2)的悬浊液通过离心分离得到沉淀物；
    (4)用蒸馏水洗涤步骤(3)的沉淀物，直到残留水的最终pH达到8.4；然后将所得沉淀物烘干，即得到所述的复合材料。
  2. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的活性炭、氯化钙和水的质量比为1-3：13：30。
  3. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的活性炭、氨水、聚乙二醇的质量体积比，以g/mL计，为1-3：15：120。
  4. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的过氧化氢的浓度为30％，滴加速率为每分钟3滴。
  5. 根据权利要求1的制备方法，其特征在于，步骤(1)中活性炭和过氧化氢的质量体积比，以g/mL计，为1-3：15。
  6. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的搅拌均匀的具体参数设置为：搅拌速度为180rpm，搅拌时间为30min。
  7. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的活性炭、氯化钙和水的质量比为2：13：30；所述的活性炭、氨水、聚乙二醇的质量体积比为2：15：120。
  8. 根据权利要求1的制备方法，其特征在于，步骤(4)所述的烘干具体为80℃真空烘箱烘干2-4h。
  9. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的活性炭为预处理之后的，预处理活性炭的制备方法为：将活性炭使用0.5-1.5mol·L -1的盐酸浸泡1.5-2.5h后，用去离子水反复冲洗至中性，再用0.5-1.5mol·L -1氢氧化钠浸泡1.5-2.5h后，用去离子水反复冲洗至中性，去除杂质后，105℃烘箱烘干，研磨后过200目筛。
  10. 根据权利要求1的制备方法，其特征在于，步骤(1)所述的氨水的浓度为1mol·L -1。
  11. 根据权利要求1的制备方法，其特征在于，步骤(2)所述的氢氧化钠溶液的pH为13。
  12. 权利要求1-11任一项所述的制备方法得到的复合材料。
  13. 权利要求12所述的复合材料在黑臭地表水环境应急处理中的应用。
  14. 根据权利要求13所述的应用，其特征在于，权利要求12所述的复合材料在黑臭地表水中的投加量为150mg/L。
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