WO2021036855A1 - 一种利用蓝藻制备反硝化外加碳源的方法和应用 - Google Patents

一种利用蓝藻制备反硝化外加碳源的方法和应用 Download PDF

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WO2021036855A1
WO2021036855A1 PCT/CN2020/109661 CN2020109661W WO2021036855A1 WO 2021036855 A1 WO2021036855 A1 WO 2021036855A1 CN 2020109661 W CN2020109661 W CN 2020109661W WO 2021036855 A1 WO2021036855 A1 WO 2021036855A1
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denitrification
cyanobacteria
carbon source
anaerobic
fermentation broth
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French (fr)
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赵明星
李子阳
施万胜
阮文权
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江南大学
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5254—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using magnesium compounds and phosphoric acid for removing ammonia
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • 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
    • C02F3/28—Anaerobic digestion processes
    • 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
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C02F3/305—Nitrification and denitrification treatment characterised by the denitrification

Definitions

  • the invention relates to a method and application for preparing an additional carbon source for denitrification by using cyanobacteria, in particular to a technology for recovering nitrogen and phosphorus in an anaerobic fermentation broth of cyanobacteria as an additional carbon source, and belongs to the treatment and utilization of solid organic waste and water treatment Technical field.
  • Cyanobacteria have a high content of organic matter and are ideal substrates for anaerobic fermentation. Through anaerobic fermentation, the organic matter in cyanobacteria is converted into volatile fatty acids (VFAs), and products with economic value can be obtained, so that the cyanobacteria can be utilized as resources. However, the subsequent utilization of cyanobacteria anaerobic fermentation products still needs to be studied.
  • Denitrification of sewage is one of the key factors in meeting the ever-increasing sewage discharge standards.
  • Municipal sewage treatment plants usually add commercial external carbon sources (methanol, acetic acid, sodium acetate, ethanol, etc., that is, substances that can provide carbon sources through external methods) to meet the C/N ratio required for denitrification, and then pass biological Denitrification treatment makes it meet the sewage discharge standard.
  • commercial carbon sources methanol, acetic acid, sodium acetate, ethanol, etc., that is, substances that can provide carbon sources through external methods
  • the addition of commercial carbon sources has greatly increased the operating costs of urban sewage treatment plants, so it is necessary to find suitable alternative carbon sources.
  • cellulosic solid carbon sources as alternative carbon sources, such as ginkgo biloba, camphor leaves, calamus, reed flowers, straw, wood chips, bark, pine branches and peanut shells.
  • Pretreatment the operation process is more complicated.
  • the denitrification effect of some carbon sources is poor.
  • the denitrification rate of bark and aloe flowers is only 12.94% and 66.11%.
  • the solid alternative carbon source loses compared with the liquid carbon source. Easy to use, fast response speed and other advantages.
  • the struvite (magnesium ammonium phosphate, MgNH 4 PO 4 ⁇ 6H 2 O) precipitation method can simultaneously recover N and P in the fermentation products of cyanobacteria, with rapid reaction and simple operation, and struvite can also be used directly or indirectly for agriculture , Forestry high-quality fertilizer is a high-quality slow-release fertilizer.
  • the struvite precipitation method has broad application prospects because of its good economic and environmental benefits, and is currently a research hotspot in the realization of recycling of sewage nitrogen and phosphorus.
  • Calcium phosphate precipitation is currently the main process for recovering phosphorus.
  • Calcium phosphate is the main component of phosphate rock.
  • the recovered calcium phosphate can be directly used as an industrial raw material for phosphate.
  • the present invention provides a method and application for recovering nitrogen and phosphorus in the cyanobacteria fermentation broth and using them as an external carbon source.
  • the invention adopts the combined process of struvite precipitation + calcium phosphate precipitation to recover nitrogen and phosphorus in the cyanobacteria anaerobic fermentation broth, and the treated cyanobacteria anaerobic fermentation broth can replace the traditional commercial carbon source as an additional carbon source in the denitrification process , And can significantly improve the denitrification capacity of sewage compared with commercial carbon sources.
  • the present invention provides a method for preparing an external carbon source from a cyanobacteria fermentation broth, and the method includes the following steps:
  • the supernatant is obtained by solid-liquid separation, adjust the pH of the supernatant to 8-11, add calcium source, the molar ratio of calcium/phosphorus Ca/P element is 1.67 ⁇ 10.02, and precipitate 15-30min ;
  • the external carbon source is a substance that can provide a carbon source in an external manner.
  • the phosphorus source is one or more of potassium dihydrogen phosphate, dipotassium hydrogen phosphate or sodium dihydrogen phosphate; the magnesium source is one or both of magnesium chloride or magnesium sulfate. kind.
  • the calcium source is one or both of calcium chloride and calcium sulfate.
  • mechanical stirring is required during the precipitation process, and the stirring rate is 300-400 rpm.
  • the solid-liquid separation is filtration or centrifugal separation.
  • the cyanobacteria anaerobic fermentation broth is produced by cyanobacteria through anaerobic acid-producing fermentation.
  • the method for producing the cyanobacteria anaerobic fermentation broth is preferably: treating the salvaged cyanobacteria in a hot alkaline solution with a pH of 12-13 and a temperature of 105-115°C for 2-3 hours, Afterwards, the anaerobic granular sludge pretreated at 105-120°C for 2-3h is added to the above-mentioned treated cyanobacteria for anaerobic fermentation to produce acid.
  • the solid-liquid separation and the supernatant can be used to obtain the cyanobacteria anaerobic Acid production fermentation broth, in which the mass ratio of anaerobic granular sludge to cyanobacteria pretreatment broth is 1-2:5.
  • the base is preferably NaOH.
  • the fermentation time for the anaerobic fermentation to produce acid is 5-20 days.
  • the present invention also provides the external carbon source prepared by the above method.
  • the present invention also provides the application of the above-mentioned external carbon source in denitrification treatment, and the denitrification treatment includes a denitrification or total denitrification treatment process.
  • the present invention also provides a method for denitrification and denitrification of domestic sewage, which uses the above-mentioned external carbon source as the carbon source.
  • the method specifically includes the following steps: mixing domestic sewage with activated sludge for denitrification and denitrification; wherein, the mixed liquid suspended solids (MLSS) of the reaction system ) Is 3000-3500mg/L, the pH is 7.0-7.5, and the above-mentioned external carbon source is added to the reaction system, and the dosage is 50-55mg COD/L.
  • the mixed liquid suspended solids (MLSS) of the reaction system ) Is 3000-3500mg/L
  • the pH is 7.0-7.5
  • the above-mentioned external carbon source is added to the reaction system, and the dosage is 50-55mg COD/L.
  • the reaction temperature of the denitrification and denitrification system is 35-37°C.
  • the denitrification and denitrification requires mechanical stirring at a rate of 130-150 rpm.
  • the denitrification and denitrification time is 0-360 min (greater than 0 and less than or equal to 360 min).
  • the present invention uses struvite precipitation method + calcium phosphate precipitation method to recover nitrogen and phosphorus in cyanobacteria anaerobic fermentation products.
  • Struvite precipitation and calcium phosphate are a chemical reaction process. The reaction is carried out at room temperature and the reaction time is short. The reaction is rapid, the operation is convenient, and the struvite formed by precipitation can be directly or indirectly used as a high-quality fertilizer for agriculture and forestry. It is a high-quality slow-release fertilizer; calcium phosphate is the main component of phosphate rock, and the recovered calcium phosphate can be used directly or indirectly as a high-quality fertilizer for agriculture and forestry. Directly used as an industrial raw material for phosphate.
  • the cyanobacteria anaerobic acid production fermentation broth contains a large amount of VFAs, which is a bioavailable carbon source.
  • the present invention uses the treated cyanobacteria anaerobic acid production fermentation broth as the carbon source for denitrification and denitrification of domestic sewage. Improve its denitrification efficiency.
  • the present invention uses the cyanobacteria anaerobic fermentation acid production product as the carbon source for denitrification and denitrification, which can not only realize the resource utilization of cyanobacteria, but also solve the problem of insufficient carbon sources in urban sewage treatment plants and reduce the operation of urban sewage treatment plants. Cost, changing "waste” into “treasure”, kills two birds with one stone.
  • Figure 1 is a process flow diagram of the present invention.
  • Figure 2 shows the effect of pH on struvite precipitation and recovery of ammonia nitrogen in cyanobacteria fermentation broth.
  • Figure 3 shows the effect of the molar ratio of Mg and N on the recovery of ammonia nitrogen from cyanobacteria fermentation liquid by struvite.
  • Figure 4 shows the effect of the molar ratio of P and N on the recovery of ammonia nitrogen from the cyanobacteria fermentation broth by struvite.
  • Figure 5 shows the effect of pH on the recovery of residual phosphorus in cyanobacteria fermentation broth with calcium phosphate.
  • Figure 6 shows the effect of the molar ratio of Ca and P on the recovery of residual phosphorus in the cyanobacteria fermentation broth with calcium phosphate.
  • Figure 7 shows the removal effect of cyanobacteria fermentation broth as carbon source for denitrification of domestic sewage.
  • Example 1 Anaerobic fermentation of cyanobacteria to produce acid
  • cyanobacteria pretreated with hot alkali and anaerobic granular sludge are mixed to produce acid by anaerobic fermentation.
  • the specific implementation steps are as follows:
  • the cyanobacteria are first pretreated with hot alkali (pH 12, temperature is 105°C, time is 2h) to obtain cyanobacteria pretreatment solution.
  • hot alkali pH 12, temperature is 105°C, time is 2h
  • cyanobacteria pretreatment solution Take a 500mL reaction flask, add 300mL cyanobacteria pretreatment solution, add seed mud at a ratio of 1:5 to the mass of the substrate, purge the reaction flask with high-purity nitrogen for 5 minutes to maintain an anaerobic environment, and react in a shaker at 37°C and 130rpm , Fermentation time is 10d. After the fermentation mixture was centrifuged (8000 rpm, 10 min), the supernatant was taken and placed in a refrigerator at 4° C. for later use.
  • Table 1 The properties of cyanobacteria anaerobic acid production fermentation broth are shown in Table 1.
  • the content of volatile fatty acids is as high as 28413mg ⁇ L -1 , and the ratio of VFAs to COD is 77.55%.
  • the contents of NH 4 + -N and water-soluble phosphorus (PO 4 3- -P) are 2790.54 and 50.16 mg ⁇ L -1 , respectively, and the ratio of COD/TN is 10.08.
  • Example 2 The effect of different pH values on the recovery of ammonia nitrogen in cyanobacteria anaerobic acid production fermentation broth by struvite precipitation method
  • Figure 2 shows the effect of struvite precipitation method on the recovery of ammonia nitrogen in cyanobacteria fermentation broth under different pH conditions. It can be seen that with the increase of pH, the removal rate of ammonia nitrogen first increases and then decreases. When the pH increased from 8 to 9, the removal rate of ammonia nitrogen increased from 62.12% to 85.84%. When the pH continues to increase, the removal rate of ammonia nitrogen gradually decreases, from 85.84% to 51.67%. Therefore, the optimal pH value determined by the present invention is 9.
  • Example 3 Effect of different molar ratios of Mg and N on struvite recovery from cyanobacteria anaerobic acid production fermentation liquid ammonia nitrogen
  • Example 2 adjust the pH of the solution to 9 with 6M sodium hydroxide solution, fix the dosage of potassium dihydrogen phosphate, where the molar ratio of P/N is 1/1, change the dosage of magnesium chloride hexahydrate Dosing amount, react under the conditions of Mg/N molar ratio of 0.8/1, 1/1, 1.1/1, 1.2/1, 1.4/1, 1.6/1, 1.8/1, using a magnetic stirrer at 300 rpm Stir, react for 30 minutes, stand for 30 minutes, and take the supernatant to determine various indicators.
  • Figure 3 shows the effect of struvite precipitation on recovery of ammonia nitrogen from cyanobacteria anaerobic acid production fermentation broth under different molar ratios of Mg and N. It can be seen that as the molar ratio of Mg to N increases, the removal rate of ammonia nitrogen increases significantly. When the molar ratio of Mg/N increases from 0.8/1 to 1.2/1, the removal rate of ammonia nitrogen increases from 67.48% to 90.08%; continue to increase the molar ratio of Mg/N, the removal rate of ammonia nitrogen does not increase significantly, when Mg/N With a molar ratio of 1.8/1, the removal rate of ammonia nitrogen is 90.91%.
  • the present invention proposes to adopt a molar ratio of Mg/N of 1.2/1 in the actual operation process.
  • Example 4 Effect of different molar ratios of P and N on struvite recovery of cyanobacteria anaerobic acid production fermentation liquid ammonia nitrogen
  • Examples 1 and 2 adjust the pH of the solution to 9 with 6M sodium hydroxide solution, fix the dosage of magnesium chloride hexahydrate, where the molar ratio of Mg/N is 1.2/1, change the potassium dihydrogen phosphate
  • the dosing amount of P/N is respectively 0.8/1, 0.9/1, 1/1, 1.1/1, 1.2/1, 1.4/1 under the conditions of P/N molar ratio, and the reaction is carried out with a magnetic stirrer at 300 rpm. After 30 minutes, let it stand for 30 minutes, and take the supernatant to determine various indicators.
  • Figure 4 shows the effect of struvite precipitation on the recovery of ammonia nitrogen in the cyanobacteria anaerobic acid production fermentation broth under the conditions of different P and N molar ratios. It can be seen that as the molar ratio of P and N increases, the removal rate of ammonia nitrogen increases significantly. When the P/N molar ratio increased from 0.8/1 to 1.1/1, the removal rate of ammonia nitrogen increased from 76.33% to 87.39%; continued to increase the P/N molar ratio, the ammonia nitrogen removal rate did not change significantly. Since increasing the P/N molar ratio will correspondingly increase the dosage of potassium dihydrogen phosphate, considering economy, the present invention proposes to adopt a P/N molar ratio of 1.1/1 in the actual operation process.
  • Example 5 Effect of different pH values on the recovery of residual phosphorus in cyanobacteria anaerobic acid production fermentation broth by calcium phosphate precipitation method
  • Figure 5 shows the recovery of residual phosphorus in cyanobacteria anaerobic acid production fermentation broth using calcium phosphate precipitation method under different pH conditions. It can be seen that as the pH value increases, the removal rate of ammonia nitrogen increases significantly. When the pH value increased from 8 to 10, the removal rate of phosphorus increased from 33.6% to 95.1%. Continue to increase the pH value, the removal rate of ammonia nitrogen does not change significantly, when the pH value is 11, the removal rate of phosphorus is 95.63%, only an increase of 0.53%. Since increasing the pH will consume more sodium hydroxide, from an economic point of view, the present invention proposes to use a pH value of 10 in the actual operation process.
  • Example 6 Effect of different molar ratios of Ca and P on the recovery of residual phosphorus in cyanobacteria anaerobic acid production fermentation broth by calcium phosphate precipitation method
  • Example 5 adjust the pH of the solution to 10 with 6M sodium hydroxide solution, add calcium chloride dihydrate, and the molar ratios of Ca/P are 1.67/1, 3.34/1, 5.01/1, respectively. Under the conditions of 6.68/1, 8.35/1, and 10.02/1, stir with a magnetic stirrer at 300 rpm, react for 15 minutes, and let stand for 30 minutes. Take the supernatant to determine various indicators.
  • Figure 6 shows the effect of calcium phosphate precipitation method on recovering residual phosphorus in cyanobacteria anaerobic acid production fermentation broth under different Ca and P molar ratios. It can be seen that as the molar ratio of Ca to P increases, the removal rate of ammonia nitrogen increases significantly. When the molar ratio of Ca to P increased from 1.67 to 6.68, the removal rate of phosphorus increased from 80.41% to 88.54%. Continuing to increase the molar ratio of Ca and P, the increase in the removal rate of phosphorus becomes smaller. When the molar ratio of Ca to P is 10.02, the removal rate of phosphorus is 89.35%, which is only an increase of 0.81%. Since the molar ratio of Ca to P needs to be added more calcium chloride dihydrate, from an economic point of view, the present invention proposes to use a molar ratio of Ca to P of 6.68 in the actual operation process.
  • Example 7 Recovery of nitrogen and phosphorus in cyanobacteria anaerobic acid production fermentation broth by combined processes under optimal conditions
  • the best process conditions for struvite precipitation method are pH 9 and the molar ratio of Mg/P/N is 1.2/1.1/1; refer to Examples 5 and 6, calcium phosphate precipitation method
  • the best process conditions are pH 10, and the molar ratio of Ca/P is 6.68.
  • Table 2 shows the effect of the combined process on the recovery of ammonia nitrogen in the cyanobacteria anaerobic acid production fermentation broth under the optimal conditions.
  • Ammonia nitrogen (NH 4 + -N), water-soluble phosphorus (SOP), TN, and TP were reduced from 1974.59 mg ⁇ L -1 , 50.16 mg ⁇ L -1 , 2821.1 mg ⁇ L -1 , 62.77 mg ⁇ L -1 to 22.83mg ⁇ L -1, 2.7mg ⁇ L -1, 550.16mg ⁇ L -1, 8.02mg ⁇ L -1, respectively, the removal rate of 98.84%, 94.62%, 80.5%, 87.22%.
  • Example 8 The removal effect of nitrate and nitrogen when the treated cyanobacteria anaerobic acid production fermentation broth is used as an external carbon source for denitrification of domestic sewage
  • Figure 7 shows the removal effect of nitrate and nitrogen when the cyanobacteria anaerobic acid production fermentation broth after nitrogen and phosphorus recovery is used as a carbon source for denitrification of domestic sewage. It can be seen that when the cyanobacteria anaerobic acid production fermentation broth after nitrogen and phosphorus recovery is used as the denitrification carbon source, the concentration of NO 3 - N in the domestic sewage is reduced from the initial 30 mg ⁇ L -1 to 0.26 mg ⁇ L -1 . The removal rate is 99.13%, and NO 3 -- N is almost completely removed.
  • the removal rate of NO 3 -- N is 78.53%; when no carbon source is added, the removal rate of NO 3 -- N is only 39.94%. It can be found that when the cyanobacteria anaerobic acid production fermentation broth after nitrogen and phosphorus recovery is used as the carbon source for denitrification, the removal rate of NO 3 -- N is increased by 59.19 respectively by comparing with no carbon source and using ethanol as the carbon source. % And 20.6%, indicating that the cyanobacteria fermentation broth is rich in bioavailable carbon sources, which can be used as carbon sources for enhanced denitrification and denitrification.
  • the cyanobacteria anaerobic acid production fermentation broth is only subjected to struvite precipitation (precipitation process: pH 9, Mg/P/N molar ratio 1.2/1.1/1) to obtain fermentation broth used as domestic sewage denitrification
  • the external carbon source was subjected to the denitrification treatment of domestic sewage according to the method of Example 8 for comparative analysis. It can be found that when the cyanobacteria anaerobic acid production fermentation broth after struvite precipitation is used as the denitrification carbon source, the concentration of NO 3 -- N in the domestic sewage is reduced from the initial 30 mg ⁇ L -1 to 6.9 mg ⁇ L -1 , the removal rate is 77.0%. Compared with the cyanobacteria anaerobic acid-producing fermentation broth used as an exogenous carbon source (99.13%) after struvite + calcium phosphate combined removal, the removal rate of NO 3 -- N was reduced by 22.32%.
  • the cyanobacteria anaerobic acid production fermentation broth is only subjected to calcium phosphate precipitation (precipitation process: pH 10, Ca/P molar ratio 6.68), and the fermentation broth obtained is used as an external carbon source for denitrification of domestic sewage.
  • the method of Example 8 is used for denitrification treatment of domestic sewage, and comparative analysis is carried out. It can be found that when the cyanobacteria anaerobic acid production fermentation broth after only calcium phosphate precipitation is used as the denitrification carbon source, the concentration of NO 3 -- N in the domestic sewage is reduced from the initial 30 mg ⁇ L -1 to 9.4 mg ⁇ L -1 , the removal rate is 68.7%. Compared with the cyanobacteria anaerobic acid production fermentation broth used as an exogenous carbon source (99.13%) after struvite + calcium phosphate combined removal, the removal rate of NO 3 -- N was reduced by 30.7%.

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Abstract

本发明公开了一种利用蓝藻制备反硝化外加碳源的方法和应用，属于固体有机废物的处理与利用和水处理技术领域。本发明是采用鸟粪石沉淀+磷酸钙沉淀组合工艺回收蓝藻厌氧发酵液中的氮磷，经处理后的蓝藻厌氧发酵液能够替代传统的商业碳源作为脱氮过程中的外加碳源，不但能够为反硝化过程提供碳源，且相对于商用碳源能够明显提高污水的脱氮能力，既可以实现蓝藻的资源化利用，又可以解决城市污水处理厂碳源不足的问题，降低城市污水处理厂运行成本，变"废"为"宝"，一举两得。

Description

一种利用蓝藻制备反硝化外加碳源的方法和应用 技术领域
本发明涉及一种利用蓝藻制备反硝化外加碳源的方法和应用，具体涉及一种回收蓝藻厌氧发酵液中氮磷后作为外加碳源的技术，属于固体有机废物的处理与利用和水处理技术领域。
背景技术
近几十年来，随着我国工业化进程的加快和社会经济的快速发展，大量含氮、磷废水排入水体，使得我国淡水湖之一的太湖处于富营养化水平。湖泊富营养化导致蓝藻大面积爆发，危机饮用水安全，破坏生态环境和自然景观，引起了极大的环境问题。太湖蓝藻的处理处置及其资源化利用成为亟需解决的问题。目前，国内外蓝藻的利用方式主要有提取有用物质、制成生物柴油、生产沼气、做有机肥料等，但是产品附加值较低，需要开发附加值更高的蓝藻资源化技术。蓝藻的有机质含量高，是厌氧发酵的理想底物。通过厌氧发酵将蓝藻中的有机质转化为挥发性脂肪酸(VFAs)，可以获得具有经济价值的产品，使蓝藻得到资源化利用。但对于蓝藻厌氧发酵产物的后续利用还需要继续研究。
污水的脱氮是满足不断提升的污水排放标准的关键因素之一。然而在我国许多城市，生活污水中的可利用碳源的不足严重制约了氮的有效去除。城市污水处理厂通常投加商用的外加碳源(甲醇、乙酸、乙酸钠、乙醇等，即能够通过外加的方式提供碳源的物质)来满足脱氮所需的C/N比，再通过生物脱氮处理使其达到污水排放标准。但是，投加商用碳源大大增加了城市污水处理厂的运行成本，因此需要寻找合适的替代碳源。有研究将纤维素类固体碳源作为替代碳源，如银杏叶、香樟叶、菖蒲、芦苇花、秸秆、木屑、树皮、松枝和花生壳等，但是利用该类碳源时，首先需要预处理，操作过程较复杂，其次有些碳源的脱氮效果较差，如树皮和芦荟花的脱氮率只有12.94％和66.11％，此外，固体替代碳源相比于液体碳源失去了易利用，反应速度快等优势。
鸟粪石(磷酸铵镁，MgNH 4PO 4·6H 2O)沉淀法可以同时回收蓝藻发酵产物中的N、P，反应迅速，操作简单，并且鸟粪石还可直接或间接被用作农业、林业优质肥料，是一种优质的缓释肥。鸟粪石沉淀法因为其良好的经济及环境效益，拥有广阔的应用前景，是当前污水脱氮除磷实现资源化的一个研究热点。
磷酸钙沉淀法(CP)是目前回收磷的主要工艺，磷酸钙是磷矿石的主要成分，回收的磷酸钙可直接用作磷酸盐的工业原料。
发明内容
为了进一步提高蓝藻厌氧发酵液的价值，以及减少商用碳源的应用，本发明提供了一种回收蓝藻发酵液中氮磷并将其作为外加碳源的方法以及应用。本发明是采用鸟粪石沉淀+磷酸钙沉淀组合工艺回收蓝藻厌氧发酵液中的氮磷，经处理后的蓝藻厌氧发酵液能够替代传统的商业碳源作为脱氮过程中的外加碳源，且相对于商用碳源能够明显提高污水的脱氮能力。
首先，本发明提供了一种从蓝藻发酵液制备外加碳源的方法，所述方法包括以下步骤：
(1)调节蓝藻厌氧发酵液的pH为8～11，投加磷源和镁源，其中，磷/氮P/N、镁/氮Mg/N元素的摩尔比分别为0.8～1.4、0.8～1.8，沉淀30-60min；
(2)沉淀结束后，固液分离获得上清液，调节上清液的pH为8～11，投加钙源，钙/磷Ca/P元素的摩尔比为1.67～10.02，沉淀15-30min；
其中，所述外加碳源即能够通过外加的方式提供碳源的物质。
在本发明的一种实施方式中，所述磷源为磷酸二氢钾、磷酸氢二钾或磷酸二氢钠中一种或几种；所述镁源为氯化镁或硫酸镁的一种或两种。
在本发明的一种实施方式中，所述钙源为氯化钙或硫酸钙的一种或两种。
在本发明的一种实施方式中，所述沉淀的过程中需要进行机械搅拌，搅拌速率为300-400rpm。
在本发明的一种实施方式中，步骤(2)中，所述固液分离为过滤或离心分离。
在本发明的一种实施方式中，所述蓝藻厌氧发酵液为蓝藻经过厌氧产酸发酵产生的。
在本发明的一种实施方式中，所述蓝藻厌氧发酵液产生的方法优选为：将打捞的蓝藻在pH＝12-13、温度为105-115℃的热碱溶液中处理2-3h，之后将105-120℃下加热预处理2-3h的厌氧颗粒污泥加入到上述经过处理的蓝藻中进行厌氧发酵产酸，发酵结束之后固液分离取上清液即可得到蓝藻厌氧产酸发酵液，其中，厌氧颗粒污泥与蓝藻预处理液的质量比为1-2：5。
在本发明的一种实施方式中，所述碱优选为NaOH。
在本发明的一种实施方式中，所述厌氧发酵产酸的发酵时间为5～20天。
其次，本发明还提供了上述方法制备得到的外加碳源。
再者，本发明还提供了上述外加碳源在脱氮处理中的应用，所述脱氮处理包括反硝化或全脱氮处理过程。
最后，本发明还提供了一种生活污水的反硝化脱氮方法，所述方法以上述外加碳源作为碳源。
在本发明的一种实施方式中，所述方法具体包括以下步骤：将生活污水与活性污泥混合， 进行反硝化脱氮；其中，反应体系的混合液悬浮固体浓度(mixed liquor suspended solids，MLSS)为3000-3500mg/L，pH为7.0-7.5，在反应体系中投加上述外加碳源，投加量为50-55mg COD/L。
在本发明的一种实施方式中，所述反硝化脱氮体系的反应温度为35-37℃。
在本发明的一种实施方式中，所述反硝化脱氮需要机械搅拌，速率是130-150rpm。
在本发明的一种实施方式中，所述反硝化脱氮时间为0～360min(大于0且小于等于360min)。
有益效果：
(1)本发明通过鸟粪石沉淀法+磷酸钙沉淀法回收蓝藻厌氧发酵产物中的氮磷，鸟粪石沉淀和磷酸钙是一个化学反应过程，反应在室温下进行，反应时间短，反应迅速，操作方便，并且沉淀形成的鸟粪石可直接或间接被用作农业、林业优质肥料，是一种优质的缓释肥；磷酸钙是磷矿石的主要成分，回收的磷酸钙可直接用作磷酸盐的工业原料。
(2)蓝藻厌氧产酸发酵液中含有大量的VFAs，是可生物利用的碳源，本发明将经处理后的蓝藻厌氧产酸发酵液作为生活污水反硝化脱氮的碳源，显著提高了其脱氮的效率。
(3)本发明将蓝藻厌氧发酵产酸产物作为反硝化脱氮的碳源，既可以实现蓝藻的资源化利用，又可以解决城市污水处理厂碳源不足的问题，降低城市污水处理厂运行成本，变“废”为“宝”，一举两得。
附图说明
图1为本发明工艺流程图。
图2为pH对鸟粪石沉淀回收蓝藻发酵液中氨氮的影响。
图3为Mg、N摩尔比对鸟粪石回收蓝藻发酵液氨氮中的影响。
图4为P、N摩尔比对鸟粪石回收蓝藻发酵液中氨氮的影响。
图5为pH对磷酸钙回收蓝藻发酵液中剩余磷的影响。
图6为Ca、P摩尔比对磷酸钙回收蓝藻发酵液中剩余磷的影响。
图7为蓝藻发酵液作为生活污水反硝化碳源时硝态氮的去除效果。
具体实施方式
实施例1：蓝藻厌氧发酵产酸
本实施例将经热碱预处理的蓝藻与厌氧颗粒污泥混合进行厌氧发酵产酸，具体实施步骤如下：
蓝藻先经热碱预处理(pH 12，温度为105℃，时间为2h)得到蓝藻预处理液。取500mL反应瓶，加入300mL蓝藻预处理液，按与底物质量比1：5加入种泥，反应瓶内采用高纯氮 吹扫5min以保持厌氧环境，在37℃、130rpm摇床内反应，发酵时间为10d。发酵混合物离心(8000rpm，10min)后取上清液，放置于4℃冰箱备用。蓝藻厌氧产酸发酵液的性质见表1。
蓝藻厌氧产酸发酵液中，挥发性脂肪酸的含量高达28413mg·L -1，VFAs与COD的比值为77.55％。NH 4 +-N和水溶性磷(PO 4 3--P)的含量分别为2790.54和50.16mg·L -1，COD/TN的比率为10.08。
表1 蓝藻厌氧产酸发酵液的性质
Figure PCTCN2020109661-appb-000001
实施例2：不同pH值对鸟粪石沉淀法回收蓝藻厌氧产酸发酵液中氨氮的影响
取200mL蓝藻厌氧产酸发酵液于500mL烧杯中，投加磷酸二氢钾和六水合氯化镁使Mg/P/N的摩尔比为1/1/1，用6M氢氧化钠溶液调节溶液的pH，分别调节pH值为8、8.5、9、9.5、10、10.5、11，用磁力搅拌器以300rpm进行搅拌，反应30min，静置30min，取上清液测定各项指标。
图2为不同pH值条件下鸟粪石沉淀法回收蓝藻发酵液中氨氮的效果。可见，随着pH的增加，氨氮的去除率先增加后降低。当pH从8升高到9时，氨氮的去除率从62.12％增加到85.84％。当继续升高pH，氨氮的去除率逐渐降低，由85.84％减少到51.67％。因此，本发明确定的最佳pH值为9。
实施例3：不同Mg、N摩尔比对鸟粪石回收蓝藻厌氧产酸发酵液氨氮中的影响
参照实施例2的操作步骤，用6M氢氧化钠溶液调节溶液的pH为9，固定磷酸二氢钾的投加量，其中，P/N的摩尔比为1/1，改变六水合氯化镁的用量投加量，分别在Mg/N的摩尔比为0.8/1、1/1、1.1/1、1.2/1、1.4/1、1.6/1、1.8/1条件下反应，用磁力搅拌器以300rpm进行搅拌，反应30min，静置30min，取上清液测定各项指标。
图3为不同Mg、N摩尔比条件下鸟粪石沉淀回收蓝藻厌氧产酸发酵液中氨氮的效果。可见，随着Mg、N摩尔比的升高，氨氮的去除率明显增加。当Mg/N的摩尔比从0.8/1增加到1.2/1时，氨氮的去除率从67.48％提高到90.08％；继续增加Mg/N的摩尔比，氨氮去除率提高不明显，当Mg/N的摩尔比为1.8/1，氨氮的去除率为90.91％，与Mg/N的摩尔比为0.8/1相比，氨氮的去除率仅增加了0.83％。由于增加Mg/N的摩尔比相应会提高六水合氯化镁的投加量，考虑经济性，本发明建议在实际操作过程中采用Mg/N的摩尔比为1.2/1。
实施例4：不同P、N摩尔比对鸟粪石回收蓝藻厌氧产酸发酵液氨氮的影响
参照实施例1，2的操作步骤，用6M氢氧化钠溶液调节溶液的pH为9，固定六水合氯化镁的投加量，其中，Mg/N的摩尔比为1.2/1，改变磷酸二氢钾的投加量分别在P/N的摩尔比为0.8/1、0.9/1、1/1、1.1/1、1.2/1、1.4/1条件下反应，用磁力搅拌器以300rpm进行搅拌，反应30min，静置30min，取上清液测定各项指标。
图4为不同P、N摩尔比条件下鸟粪石沉淀回收蓝藻厌氧产酸发酵液中氨氮的效果。可见，随着P、N摩尔比的升高，氨氮的去除率明显增加。当P/N的摩尔比从0.8/1增加到1.1/1时，氨氮的去除率从76.33％增加到87.39％；继续增加P/N的摩尔比，氨氮去除率变化不明显。由于增加P/N的摩尔比相应会提高磷酸二氢钾的投加量，考虑经济性，本发明建议在实际操作过程中采用P/N的摩尔比为1.1/1。
实施例5：不同pH值对磷酸钙沉淀法回收蓝藻厌氧产酸发酵液中剩余磷的影响
取200mL经鸟粪石沉淀法处理后的蓝藻厌氧产酸发酵液于500mL烧杯中(其中鸟粪石沉淀过程中的pH为9，Mg/N的摩尔比为1.2/1，P/N的摩尔比为1.1/1)，投加二水合氯化钙使得Ca/P的摩尔比为1.67/1，用6M氢氧化钠溶液调节溶液的pH，分别在pH值为8、8.5、9、9.5、10、10.5、11条件下反应，用磁力搅拌器以300rpm进行搅拌，反应15min，静置30min，取上清液测定各项指标。
图5为不同pH条件下磷酸钙沉淀法回收蓝藻厌氧产酸发酵液中剩余磷的效果。可见，随着pH值的升高，氨氮的去除率明显增加。当pH值从8升高到10时，磷的去除率从33.6％增加到95.1％。继续提升pH值，氨氮的去除率变化不明显，当pH值为11时，磷的去除率为95.63％，仅增加了0.53％。由于增加pH会消耗更多氢氧化钠，从经济性角度出发，本发明建议在实际操作过程中采用pH值为10。
实施例6：不同Ca、P摩尔比对磷酸钙沉淀法回收蓝藻厌氧产酸发酵液中剩余磷的影响
参照实施例5的操作步骤，用6M氢氧化钠溶液调节溶液的pH为10，投加二水合氯化钙，分别在Ca/P的摩尔比为1.67/1、3.34/1、5.01/1、6.68/1、8.35/1、10.02/1条件下反应，用磁力搅拌器以300rpm进行搅拌，反应15min，静置30min，取上清液测定各项指标。
图6为不同Ca、P摩尔比条件下磷酸钙沉淀法回收蓝藻厌氧产酸发酵液中剩余磷的效果。可见，随着Ca、P摩尔比的升高，氨氮的去除率明显增加。当Ca、P摩尔比从1.67升高到6.68时，磷的去除率从80.41％增加到88.54％。继续提升Ca、P摩尔比，磷的去除率增加变小，当Ca、P摩尔比为10.02时，磷的去除率为89.35％，仅增加了0.81％。由于Ca、P摩尔比需要投加更多二水合氯化钙，从经济性角度出发，本发明建议在实际操作过程中采用Ca、P摩尔比为6.68。
实施例7:最佳条件下组合工艺回收蓝藻厌氧产酸发酵液中氮磷的效果
参照实施例3、4、5，鸟粪石沉淀法最佳的工艺条件为pH为9，Mg/P/N的摩尔比为1.2/1.1/1；参照实施例5、6，磷酸钙沉淀法最佳的工艺条件为pH为10，Ca/P的摩尔比为6.68。最佳条件下组合工艺回收蓝藻厌氧产酸发酵液中氨氮的效果见表2。
氨氮(NH 4 +-N)、水溶性磷(SOP)、TN、TP分别从1974.59mg·L -1、50.16mg·L -1、2821.1mg·L -1、62.77mg·L -1降低到22.83mg·L -1、2.7mg·L -1、550.16mg·L -1、8.02mg·L -1，去除率分别为98.84％、94.62％、80.5％、87.22％。
表2 最佳条件下组合工艺回收蓝藻厌氧产酸发酵液氮磷的效果
Figure PCTCN2020109661-appb-000002
实施例8:处理后的蓝藻厌氧产酸发酵液作为生活污水反硝化外加碳源时硝氮的去除效果
本实施例将生活污水与活性污泥进行混合进行反硝化脱氮，生活污水投加硝酸钾使其NO 3 --N的初始浓度为30mg·L -1，反应体系的混合液悬浮固体浓度(mixed liquor suspended solids，MLSS)为3000mg/L，将pH调至7.0±0.5，35±0.1℃水浴加热，机械搅拌使其充分混合。以不加外碳源作为空白组，分别投加乙醇和实施例7制备得到的经过氮磷回收后的蓝藻厌氧产酸发酵液作为碳源，投加量的外加碳源的量为50mg COD·L -1(即投加外加碳源，使得最终反应体系中，外加碳源所提供的COD的浓度为50mg COD·L -1)，对比反硝化效果，间隔取样测定硝氮的变化。实验用生活污水的性质见表3。
表3 实验用生活污水的性质
Figure PCTCN2020109661-appb-000003
图7为经过氮磷回收后的蓝藻厌氧产酸发酵液作为生活污水反硝化碳源时的硝氮的去除效果。可见，当经过氮磷回收后的蓝藻厌氧产酸发酵液作为反硝化碳源时，生活污水中的NO 3 -N的浓度由初始的30mg·L -1降低到0.26mg·L -1，去除率为99.13％，NO 3 --N基本上全部去除。当乙醇作为外加碳源时，NO 3 --N的去除率为78.53％；当不外加碳源时，NO 3 --N的去除率仅为39.94％。可以发现，利用经过氮磷回收后的蓝藻厌氧产酸发酵液作为反硝化碳源时，通过与不加碳源和利用乙醇作为碳源对比，NO 3 --N的去除率分别提高了59.19％和20.6％，表明蓝藻发酵液中富含易生物利用的碳源，可以作为强化反硝化脱氮的碳源。
对比例1
鸟粪石单独处理后蓝藻厌氧产酸发酵液作为反硝化外加碳源的效果情况
将蓝藻厌氧产酸发酵液只经过鸟粪石沉淀后(沉淀工艺为：pH为9，Mg/P/N的摩尔比为1.2/1.1/1)得到的发酵液用作生活污水反硝化的外源碳源，按照实施例8的方法进行生活污水反硝化处理，进行对比分析。可以发现，当只经鸟粪石沉淀后的蓝藻厌氧产酸发酵液作为反硝化碳源时，生活污水中的NO 3 --N的浓度由初始的30mg·L -1降低到6.9mg·L -1，去除率为77.0％。通过与经鸟粪石+磷酸钙组合去除后蓝藻厌氧产酸发酵液作为外源碳源时(99.13％)相比，NO 3 --N的去除率下降了22.32％。
对比例2
磷酸钙单独处理后蓝藻厌氧产酸发酵液作为反硝化外加碳源的效果情况
将蓝藻厌氧产酸发酵液只经过磷酸钙沉淀(沉淀工艺为：pH为10，Ca/P的摩尔比为6.68)后得到的发酵液用作生活污水反硝化的外源碳源，按照实施例8的方法进行生活污水反硝化处理，进行对比分析。可以发现，当只经磷酸钙沉淀后的蓝藻厌氧产酸发酵液作为反硝化碳源时，生活污水中的NO 3 --N的浓度由初始的30mg·L -1降低到9.4mg·L -1，去除率为68.7％。通过与经鸟粪石+磷酸钙组合去除后蓝藻厌氧产酸发酵液作为外源碳源时(99.13％)相比，NO 3 --N的去除率下降了30.7％。

Claims (13)

  1. 一种外加碳源的制备方法，其特征在于，所述方法包括以下步骤：
    (1)调节蓝藻厌氧发酵液的pH为8～11，投加磷源和镁源，其中，磷/氮、镁/氮元素的摩尔比分别为0.8～1.4、0.8～1.8，沉淀30-60min；
    (2)沉淀结束后，固液分离获得上清液，调节上清液的pH为8～11，投加钙源，钙/磷元素的摩尔比为1.67～10.02，沉淀15-30min；
    其中，所述外加碳源即能够通过外加的方式提供碳源的物质。
  2. 根据权利要求1所述的一种外加碳源的制备方法，其特征在于，所述磷源为磷酸二氢钾、磷酸氢二钾或磷酸二氢钠中一种或几种；所述镁源为氯化镁或硫酸镁的一种或两种。
  3. 根据权利要求1或2所述的一种外加碳源的制备方法，其特征在于，所述钙源为氯化钙或硫酸钙的一种或两种。
  4. 根据权利要求1或2所述的一种外加碳源的制备方法，其特征在于，所述蓝藻厌氧发酵液产生的方法为：将打捞的蓝藻在pH＝12-13、温度为105-115℃的热碱溶液中处理2-3h，之后将105-120℃下加热预处理2-3h的厌氧颗粒污泥加入到上述经过处理的蓝藻中进行厌氧发酵产酸，发酵结束之后固液分离取上清液即可得到蓝藻厌氧产酸发酵液，其中，厌氧颗粒污泥与蓝藻预处理液的质量比为1-2：5。
  5. 根据权利要求3所述的一种外加碳源的制备方法，其特征在于，所述蓝藻厌氧发酵液产生的方法为：将打捞的蓝藻在pH＝12-13、温度为105-115℃的热碱溶液中处理2-3h，之后将105-120℃下加热预处理2-3h的厌氧颗粒污泥加入到上述经过处理的蓝藻中进行厌氧发酵产酸，发酵结束之后固液分离取上清液即可得到蓝藻厌氧产酸发酵液，其中，厌氧颗粒污泥与蓝藻预处理液的质量比为1-2：5。
  6. 根据权利要求4所述的一种外加碳源的制备方法，其特征在于，所述碱为NaOH。
  7. 根据权利要求4所述的一种外加碳源的制备方法，其特征在于，所述厌氧发酵产酸的发酵时间为5～20天。
  8. 权利要求1～7任一项所述的一种外加碳源的制备方法制备得到的外加碳源。
  9. 权利要求8所述的外加碳源在脱氮处理中的应用，所述脱氮处理包括反硝化或全脱氮处理过程。
  10. 一种生活污水的反硝化脱氮方法，其特征在于，所述方法以权利要求8所述的外加碳源为碳源。
  11. 根据权利要求10所述的一种生活污水的反硝化脱氮方法，其特征在于，所述方法具体包括以下步骤：将生活污水与活性污泥混合，进行反硝化脱氮；其中，反应体系的混合液 悬浮固体浓度为3000-3500mg/L，pH为7.0-7.5，在反应体系中投加上述外加碳源，投加量为50-55mg COD/L。
  12. 根据权利要求11所述的一种生活污水的反硝化脱氮方法，其特征在于，所述反硝化脱氮体系的反应温度为35-37℃。
  13. 根据权利要求11或12所述的一种生活污水的反硝化脱氮方法，其特征在于，所述反硝化脱氮的时间为大于0且小于等于360min。
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