WO2015161577A1 - 用于处理沼液超标氮磷的膜式光生物反应器及其处理方法 - Google Patents

用于处理沼液超标氮磷的膜式光生物反应器及其处理方法 Download PDF

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WO2015161577A1
WO2015161577A1 PCT/CN2014/083294 CN2014083294W WO2015161577A1 WO 2015161577 A1 WO2015161577 A1 WO 2015161577A1 CN 2014083294 W CN2014083294 W CN 2014083294W WO 2015161577 A1 WO2015161577 A1 WO 2015161577A1
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biogas slurry
membrane
photobioreactor
microalgae
phosphorus
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French (fr)
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李清彪
陈曦
何宁
王远鹏
沈亮
王海涛
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Xiamen University
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Xiamen University
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/02—Photobioreactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/102—Permeable membranes
    • 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
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • 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
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • C02F3/1273—Submerged membrane bioreactors
    • 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
    • C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
    • C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12M23/00—Constructional details, e.g. recesses, hinges
    • C12M23/58—Reaction vessels connected in series or in parallel
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
    • C12M25/10—Hollow fibers or tubes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/16—Hollow fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2688—Biological processes
    • 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
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • 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
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to biogas slurry treatment, in particular to a membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus and a treatment method thereof.
  • biogas slurry produced by anaerobic fermentation of various organic wastes has a large amount of inorganic salt components such as ammonia nitrogen and phosphate. If it is directly discharged into the river, it will not only cause eutrophication of the water body, but also lead to the loss of a lot of beneficial nutrients. .
  • biogas slurry treatment technology can be divided into 2 Large categories: one is aerobic microbial treatment, and the other is natural biological treatment.
  • the aerobic treatment method includes an activated sludge method, a biological filter, a biological rotary contact oxidation method, and a batch activated sludge method.
  • Natural biological treatment methods mainly include: Biological pond method and constructed wetland treatment.
  • the biological pond technology is in line with China's national conditions.
  • problems including the unreasonable structure of biological ponds, low purification load, and widespread siltation problems.
  • the wetland treatment method has a large area and is difficult to be applied in places where land is scarce (Zhejiang Agricultural Sciences, 2010, 4, 872-874).
  • Algae has a unique metabolic mode, which can synthesize its own protoplasts by using solar energy and inorganic substances through photosynthesis, overcoming the drawbacks that traditional sewage treatment methods are easy to cause secondary pollution, and there are valuable potential nutrient losses, which may lead to incomplete utilization of resources. .
  • Algae can effectively and at low cost remove nutrients such as nitrogen and phosphorus that cause eutrophication of water bodies.
  • As a method of secondary treatment or advanced treatment of sewage replacement or compensation, the use of algae for nitrogen and phosphorus removal has attracted widespread attention.
  • biogas slurry usually contains a large amount of microorganisms and suspended matter, and only a few species of algae can grow normally therein.
  • the biogas slurry needs to be pretreated to remove microorganisms and suspended solids.
  • the currently used pretreatment method is to centrifuge biogas slurry, membrane filtration or ultraviolet irradiation sterilization ( Bioresour. Technol, 2011, 102, 8639-8645), but only a small amount of biogas slurry can be processed, and the energy consumption is large. It can only be used in the laboratory and cannot be used on a large scale. This has become a major obstacle to the promotion and application of microalgae using biogas slurry technology.
  • the object of the present invention is to provide a membrane photobioreactor for treating the biogas slurry exceeding the standard nitrogen and phosphorus for the purpose of reducing the inhibition of the microalgae by harmful substances and improving the absorption of nitrogen, phosphorus and the like by the microalgae.
  • Another object of the present invention is to provide a method of treating excess nitrogen and phosphorus in a biogas slurry.
  • the membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus is provided with a biogas liquid storage tank and a first peristaltic pump , microalgae culture tank, second peristaltic pump, air pump, membrane photobioreactor and hollow fiber membrane;
  • the air outlet of the air pump is connected to the microalgae culture tank, and the hollow fiber membrane is embedded in the membrane photobioreactor, and the outlet of the microalgae culture tank is connected with the inlet and outlet of the membrane photobioreactor, and the second peristalsis
  • the inlet of the pump is connected to the outlet of the membrane photobioreactor
  • the outlet of the second peristaltic pump is connected to the microalgae culture tank
  • the microalgae is circulated between the microalgae culture tank and the membrane photobioreactor by the second peristaltic pump.
  • the microalgae is outside the hollow fiber membrane in the membrane photobioreactor;
  • the biogas liquid storage tank is connected with the inlet and outlet of the upper and lower ends of the membrane photobioreactor, and the biogas slurry is driven by the first peristaltic pump in the biogas liquid storage tank
  • the circulation flows with the membrane photobioreactor, and the biogas slurry is inside the hollow fiber membrane in the membrane photobioreactor.
  • the biogas liquid storage tank can be connected to the upper and lower ends of the membrane photobioreactor through a silica gel tube having a diameter of 6 mm.
  • the microalgae culture tank can be connected to the inlet and outlet sides of the membrane photobioreactor through a silica gel tube having a diameter of 6 mm.
  • the air pump can compress air into a microalgae culture tank through a 6 mm diameter silicone tube.
  • the membrane photobioreactor is a cylindrical photobioreactor with an aspect ratio of 6-7.
  • the hollow fiber membrane may be a 0.1 ⁇ m hollow fiber membrane.
  • a method for treating excessive nitrogen and phosphorus in a biogas slurry, using the membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus, the method is as follows:
  • the biogas slurry containing excessive nitrogen and phosphorus is stored in the biogas storage tank, and is circulated and flowed in the silica gel tube by the first peristaltic pump; the microalgae solution is cultured in the microalgae culture tank, and is circulated in the silicone tube by the second peristaltic pump.
  • Flow air is introduced into the microalgae culture tank through the air pump, the biogas slurry and the microalgae solution are merged in the membrane photobioreactor, the biogas slurry flows in the hollow fiber membrane tube, and the microalgae solution is in the hollow fiber membrane tube.
  • the external circulation flows, and the two flow in opposite directions; the excess nitrogen and phosphorus in the biogas slurry are absorbed from the hollow fiber membrane through the extra-microalgae solution, and the nitrogen and phosphorus in the biogas slurry are absorbed by the periodic culture to reach the discharge standard.
  • the nitrogen and phosphorus in the biogas slurry in the liquid storage tank are absorbed, it is not necessary to replace the microalgae in the microalgae culture tank, and only the new biogas slurry needs to be replaced in the biogas liquid storage tank.
  • the biogas slurry may be a waste liquid produced by anaerobic fermentation of straw and pig manure to produce biogas, and the waste liquid generally contains up to 1000 mg/L of ammonia nitrogen and 5 g/L of solid suspension.
  • the circulation rate of the biogas slurry circulating in the silicone tube driven by the first peristaltic pump may be 40 to 60 mL/min.
  • the circulating flow rate of the microalgae solution circulating in the silicone tube driven by the second peristaltic pump may be 120-160 mL/min.
  • the amount of the introduced air may be 1 L/L ⁇ min.
  • the invention solves the problem that the harmful substances such as microorganisms and suspended solids in the biogas slurry inhibit the growth of the microalgae, and at the same time maintains the high concentration of the microalgae to accelerate the treatment rate of the biogas slurry.
  • the invention inserts a 0.1 ⁇ m hollow fiber membrane into a common column type photobioreactor, and the biogas slurry circulates through the membrane through a peristaltic pump, and the microalgae solution circulates outside the membrane by a peristaltic pump, and the microorganisms, suspended matter, etc. larger than the membrane pore diameter.
  • Hazardous substances are trapped, and nitrogen, phosphorus and other nutrients are diffused from the biogas slurry through the membrane to the microalgae to be absorbed, so as to reduce the inhibition of harmful substances on the microalgae and improve the absorption of nitrogen, phosphorus and other nutrients by the microalgae.
  • the hollow fiber membrane of the present invention can retain characteristics greater than the pore size of the material, and retain harmful substances such as microorganisms and suspended substances larger than the pore diameter thereof, and the nutrients such as nitrogen and phosphorus can be transmitted, thereby reducing the inhibition of the microalgae and promoting the inhibition thereof.
  • the purpose of growth is not limited to the pore size of the material, and retain harmful substances such as microorganisms and suspended substances larger than the pore diameter thereof, and the nutrients such as nitrogen and phosphorus can be transmitted, thereby reducing the inhibition of the microalgae and promoting the inhibition thereof. The purpose of growth.
  • the microalgae can maintain a high concentration, increase the rate of nitrogen and phosphorus absorption by the microalgae, and shorten the time for the microalgae to treat the biogas slurry.
  • the biogas slurry after 18 days of microalgae treatment can reach the national first-class discharge standard containing less than 10 mg/L of ammonia nitrogen and 0.5 mg/L of phosphate.
  • FIG. 1 is a schematic view showing the structure of an embodiment of a membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus according to the present invention.
  • the mark A is air and B is a biogas slurry.
  • FIG. 2 is a comparison of ammonia nitrogen absorption in a membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus in a conventional photobioreactor according to the present invention.
  • ⁇ is PBR and ⁇ is MPBR.
  • Figure 3 is a comparison of phosphate absorption in a membrane photobioreactor for treating biogas slurry exceeding standard nitrogen and phosphorus in a conventional photobioreactor according to the present invention.
  • the mark ⁇ is PBR
  • ⁇ is MPBR.
  • Figure 4 is a comparison of ammonia nitrogen uptake in the before and after batches of a membrane photobioreactor for treating biogas slurry exceeding standard nitrogen in continuous culture.
  • Figure 5 is a comparison of phosphate absorption in the before and after batches in a membrane photobioreactor for the treatment of biogas slurry exceeding standard nitrogen in continuous culture.
  • the membrane photobioreactor embodiment for treating biogas slurry exceeding standard nitrogen and phosphorus is provided with a biogas liquid storage tank 1 and a first peristaltic pump 2 .
  • the air outlet of the air pump 5 is connected to the microalgae culture tank 3, and the hollow fiber membrane 7 is embedded in the membrane photobioreactor 6, and the outlet of the microalgae culture tank 3 and the membrane photobioreactor 6 are at the side end.
  • the outlet is connected, the inlet of the second peristaltic pump 4 is connected to the outlet of the membrane photobioreactor 6, the outlet of the second peristaltic pump 4 is connected to the microalgae culture tank 3, and the microalgae is driven by the second peristaltic pump 4 in the microalgae culture tank.
  • the membrane photobioreactor 6 circulates between the flow, and the microalgae is outside the hollow fiber membrane 7 in the membrane photobioreactor 6; the biogas liquid storage tank 1 and the membrane photobioreactor 6 enter the upper and lower ends The outlet is connected, and the biogas slurry is circulated between the biogas storage tank 1 and the membrane photobioreactor 6 by the first peristaltic pump 2, and the biogas slurry is inside the hollow fiber membrane 7 in the membrane photobioreactor 6.
  • the mark A is air and B is a biogas slurry.
  • the biogas liquid storage tank 1 is connected to the upper and lower ends of the membrane photobioreactor 6 through a silica gel tube having a diameter of 6 mm.
  • the microalgae culture tank 3 is connected to the inlet and outlet sides of the membrane photobioreactor 6 through a silica gel tube having a diameter of 6 mm.
  • the air pump 5 compresses air into the microalgae culture tank 3 through a silicone tube having a diameter of 6 mm.
  • the membrane photobioreactor 6 is a cylindrical photobioreactor with an aspect ratio of 6-7.
  • the hollow fiber membrane 7 was a 0.1 ⁇ m hollow fiber membrane.
  • the method for treating the super-standard nitrogen and phosphorus in the biogas slurry by using the membrane photobioreactor is as follows:
  • the biogas slurry containing excessive nitrogen and phosphorus is stored in the biogas liquid storage tank 1, and is driven by the first peristaltic pump 2 to circulate in the silicone tube at a flow rate of 40 to 60. mL/min; the microalgae solution is incubated in the microalgae culture tank 3, and is circulated in the silicone tube by the second peristaltic pump 4, and the flow rate is 120-160.
  • the concentration of biogas slurry containing high concentration of ammonia nitrogen is first diluted to 128 mg/L ammonia nitrogen and 26.2 mg/L phosphate.
  • a well-mixed 1000 mL of biogas slurry was added to the biogas storage tank, and 1000 mL of a microalgae liquid containing 0.1 g/L of C. sorokiniana was added to the microalgae culture tank.
  • the whole set was placed in a light incubator, and the temperature inside the incubator was set at 25 °C, and the light intensity was 7200 Lux.
  • Air of 1 L/L ⁇ min was introduced into the microalgae culture tank by an air pump.
  • the peristaltic pump drives the microalgae to circulate outside the membrane at a circulating flow rate of 150-160 mL/min, so that the biogas slurry maintains a circulating flow of 50-60 mL/min in the hollow fiber membrane.
  • the ammonia nitrogen of the treated biogas slurry dropped to 72.2 mg/L and the phosphate decreased to 9.2 mg/L.
  • the microalgae C. sorokiniana is directly mixed with the biogas slurry in a photobioreactor (PBR ) to treat the super-standard nitrogen.
  • PBR photobioreactor
  • the ammonia nitrogen of the treated biogas slurry dropped to 102.3 mg/L
  • the phosphate decreased to 20.7 mg/L
  • the rate of treatment of the biogas slurry decreased significantly.
  • the concentration of biogas slurry containing high concentrations of ammonia nitrogen is first diluted to 128 mg/L ammonia nitrogen and 26.2 mg/L phosphate.
  • a 1000 mL of biogas slurry was added to the biogas storage tank, and 1000 mL of a microalgae liquid containing 0.1 g/L of C. sorokiniana was added to the microalgae culture tank.
  • the whole set was placed in a light incubator with a temperature of 25 ° C and an illumination intensity of 7200 Lux.
  • Air of 1 L/L ⁇ min was introduced into the microalgae culture tank by an air pump.
  • the peristaltic pump drives the microalgae to circulate outside the membrane at a circulating flow rate of 120-140 mL/min, so that the biogas slurry maintains a circulating flow of 40 to 50 mL/min in the hollow fiber membrane.
  • the parameters such as the concentration of the biogas slurry, the light, the temperature, the aeration rate, and the circulation flow rate are the same as those of the previous batch.
  • the same volume of the biogas slurry is replaced in the biogas liquid storage tank, and the microalgae culture tank is not changed, and the second batch culture is continued.
  • Mg/L, phosphate decreased to 2 mg / L, the speed of microalgae treatment of biogas slurry was significantly higher.

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Abstract

用于处理沼液超标氮磷的膜式光生物反应器及其处理方法，涉及沼液处理。所述用于处理沼液超标氮磷的膜式光生物反应器设有沼液储存罐、蠕动泵、微藻培养罐、空气泵、膜式光生物反应器和中空纤维膜。含超标氮、磷的沼液贮存在沼液储存罐中，由第 1 蠕动泵带动在硅胶管内循环流动；微藻溶液在微藻培养罐中光照培养，由第 2 蠕动泵带动在硅胶管内循环流动，透过空气泵向微藻培养罐中通入空气，沼液和微藻溶液在膜式光生物反应器中汇合，沼液在中空纤维膜管内循环流动，微藻溶液在中空纤维膜管外循环流动，两者错流流动；沼液中超标氮、磷从中空纤维膜内透过被膜外微藻溶液吸收，经过周期培养将沼液中超标氮、磷吸收，达到排放标准。

Description

用于处理沼液超标氮磷的膜式光生物反应器及其处理方法
技术领域
本发明涉及沼液处理，具体涉及一种用于处理沼液超标氮磷的膜式光生物反应器及其处理方法。
背景技术
利用各种有机物废弃物厌氧发酵后产生的沼液具有大量的氨氮、磷酸盐等无机盐成分，如果将其直接排放河流中，不但会造成水体富营养化，而且会导致大量有益养分的流失。目前，沼液处理技术可分为2 大类：一是好氧微生物处理法，二是自然生物处理法。好氧处理法包括活性污泥法、生物滤池、生物转盘接触氧化法和间歇式活性污泥法等。其工艺构筑物复杂、机械设备多、维护工作量大、投资大、能耗高、运行维护费用高，规模小的养殖场难以承受，与我国经济发展水平不相适应。自然生物处理法主要包括: 生物塘法和人工湿地处理法。生物塘技术符合我国国情， 但还存在诸多问题，包括生物塘结构不合理、净化负荷低、普遍存在淤积问题等。湿地处理法其占地面积大，在土地稀缺的地方，难以实际应用(浙江农业科学，2010,4，872-874)。
藻类具有独特的代谢方式，可通过光合作用利用太阳能和无机物合成本身的原生质，克服传统污水处理方法易引起二次污染外还存在有价值的潜在营养物质丢失、会导致资源不完全利用的弊端。藻类能够有效并低成本地去除造成水体富营养化的氮、磷等营养物质。作为一种二级处理或深度处理污水替代或弥补的方法，利用藻类脱氮除磷已引起广泛关注。然而沼液通常含有大量的微生物和悬浮物，只有少数藻种可以在其中正常生长。大部分经济藻种如果直接投入沼液中进行氮、磷等养分的吸收，其生长将会受到其不同程度的抑制( Bioresour. Technol, 2011, 102, 8639-8645)。最近的研究将培养微藻的光生物反应器和中空纤维膜相结合，但只是对藻浓度起到富集增加作用，达到增大吸收氮、磷速度的目的，还是只能利用纯净的培养液作为培养基( Bioresour. Technol, 2012, 117, 80-85; Bioresour. Technol, 2012, 125, 59-64)。
为了提高微藻对氮、磷等养分的吸收速度，并且提高经济藻种的产量，沼液需要事先预处理把其中的微生物和悬浮物去除。目前常用的预处理方法是把沼液离心、膜过滤或者紫外照射杀菌( Bioresour. Technol, 2011, 102, 8639-8645)，但只能处理少量的沼液，且耗能较大，只能在实验室中得到应用，无法大规模使用，这成为制约微藻利用沼液技术推广应用的主要障碍。
另外，传统方法中每当一批沼液处理完后，需要更换新的沼液并重新投入藻种扩大培养，使得微藻无法保持高浓度，从而导致微藻吸收沼液中氮、磷的量下降，延长了处理沼液的时间。
发明内容
本发明的目的是提供一种可达到减少有害物质对微藻的抑制，提高微藻吸收氮、磷等养分目的的用于处理沼液超标氮磷的膜式光生物反应器。
本发明的另一目的是提供一种处理沼液中超标氮磷的方法。
所述用于处理沼液超标氮磷的膜式光生物反应器设有沼液储存罐、 第1蠕动泵 、微藻培养罐、第2蠕动泵、空气泵、膜式光生物反应器和中空纤维膜；
所述空气泵的出气口接微藻培养罐，中空纤维膜内嵌在膜式光生物反应器中，微藻培养罐的出口与膜式光生物反应器侧端两进出口连接，第2蠕动泵的进口接膜式光生物反应器的出口，第2蠕动泵的出口接微藻培养罐，微藻通过第2蠕动泵的带动在微藻培养罐和膜式光生物反应器之间循环流动，并且微藻处于膜式光生物反应器中的中空纤维膜外侧；沼液储存罐与膜式光生物反应器上下两端进出口连接，沼液通过第1蠕动泵的带动在沼液储存罐和膜式光生物反应器之间循环流动，并且沼液处于膜式光生物反应器中的中空纤维膜内侧。
所述沼液储存罐可通过直径为6mm的硅胶管与膜式光生物反应器上下两端进出口连接。
所述微藻培养罐可通过直径为6mm的硅胶管与膜式光生物反应器侧端两进出口连接。
所述空气泵可通过直径为6mm的硅胶管将空气压缩通入微藻培养罐。
所述膜式光生物反应器为圆柱型光生物反应器，其高径比可为6~7。
所述中空纤维膜可采用0.1μm中空纤维膜。
一种处理沼液中超标氮磷的方法，采用所述用于处理沼液超标氮磷的膜式光生物反应器，所述方法如下：
含超标氮、磷的沼液贮存在沼液储存罐中，由第1蠕动泵带动在硅胶管内循环流动；微藻溶液在微藻培养罐中光照培养，由第2蠕动泵带动在硅胶管内循环流动，透过空气泵向微藻培养罐中通入空气，沼液和微藻溶液在膜式光生物反应器中汇合，沼液在中空纤维膜管内循环流动，微藻溶液在中空纤维膜管外循环流动，两者错流流动；沼液中超标氮、磷从中空纤维膜内透过被膜外微藻溶液吸收，经过周期培养将沼液中超标氮、磷吸收，达到排放标准，当沼液储存罐中沼液氮、磷吸收完时，无需更换微藻培养罐中微藻，只在沼液储存罐中需更换新沼液即可。
所述沼液可为秸秆、猪粪厌氧发酵产沼气后所产生的废液，所述废液一般含有高达1000mg/L的氨氮和5g/L的固体悬浮物。
所述由第1蠕动泵带动在硅胶管内循环流动的沼液循环流速可为40~60 mL/min。
所述由第2蠕动泵带动在硅胶管内循环流动的微藻溶液循环流速可为120~160mL/min。
所述通入空气的量可为1L/L∙min 。
本发明解决了沼液中微生物、悬浮物等有害物质对微藻生长起到抑制的问题，同时保持微藻的高浓度加快沼液处理速率。本发明通过普通柱型光生物反应器中嵌入0.1μm中空纤维膜，沼液通过蠕动泵在膜内循环流动，微藻溶液通过蠕动泵在膜外循环流动，大于膜孔径的微生物、悬浮物等有害物质被截留，而氮、磷等养分从沼液透过膜扩散到微藻被吸收，达到减少有害物质对微藻的抑制，提高微藻吸收氮、磷等养分的目的。
本发明具有以下突出优点：
1、本发明利用中空纤维膜能够截留大于其孔径物质的特性，截留大于其孔径的微生物、悬浮物等有害物质，而氮、磷等养分能够透过，实在了减少对微藻的抑制促进其生长的目的。
2、能够使得微藻保持较高的浓度，提高微藻吸收沼液中氮、磷的速率，缩短微藻处理沼液的时间。
3、经过微藻18天处理后的沼液，能达到含氨氮10mg/L以下、磷酸盐0.5mg/L以下的国家一级排放标准。
附图说明
图1为本发明所述用于处理沼液超标氮磷的膜式光生物反应器实施例的结构组成示意图。在图1中，标记A为空气，B为沼液。
图2为本发明所述用于处理沼液超标氮磷的膜式光生物反应器和普通光生物反应器中氨氮吸收的对比。在图2中，标记■为PBR，●为MPBR。
图 3为本发明所述用于处理沼液超标氮磷的膜式光生物反应器和普通光生物反应器中磷酸盐吸收的对比。在图3中，标记■为PBR，●为MPBR。
图4为连续培养时用于处理沼液超标氮磷的膜式光生物反应器中前后批次氨氮吸收的对比。
图 5为连续培养时用于处理沼液超标氮磷的膜式光生物反应器中前后批次磷酸盐吸收的对比。
具体实施方式
下面详细的说明仅仅是阐述本发明的普遍原理，并非限制性的，实际应用过程中可以根据不同藻种的性质，以及不同沼液的排放标准等具体情况进行合理的调整和修改。
参见图1，所述用于处理沼液超标氮磷的膜式光生物反应器实施例设有沼液储存罐1、 第1蠕动泵2 、微藻培养罐3、第2蠕动泵4 、空气泵5、膜式光生物反应器6和中空纤维膜7。
所述空气泵5的出气口接微藻培养罐3，中空纤维膜7内嵌在膜式光生物反应器6中，微藻培养罐3的出口与膜式光生物反应器6侧端两进出口连接，第2蠕动泵4的进口接膜式光生物反应器6的出口，第2蠕动泵4的出口接微藻培养罐3，微藻通过第2蠕动泵4的带动在微藻培养罐3和膜式光生物反应器6之间循环流动，并且微藻处于膜式光生物反应器6中的中空纤维膜7外侧；沼液储存罐1与膜式光生物反应器6上下两端进出口连接，沼液通过第1蠕动泵2的带动在沼液储存罐1和膜式光生物反应器6之间循环流动，并且沼液处于膜式光生物反应器6中的中空纤维膜7内侧。在图1中，标记A为空气，B为沼液。
所述沼液储存罐1通过直径为6mm的硅胶管与膜式光生物反应器6上下两端进出口连接。
所述微藻培养罐3通过直径为6mm的硅胶管与膜式光生物反应器6侧端两进出口连接。
所述空气泵5通过直径为6mm的硅胶管将空气压缩通入微藻培养罐3。
所述膜式光生物反应器6为圆柱型光生物反应器，其高径比可为6~7。
所述中空纤维膜7采用0.1μm中空纤维膜。
所述采用膜式光生物反应器处理沼液中超标氮磷的方法如下：
含超标氮、磷的沼液贮存在沼液储存罐1中，由第1蠕动泵2带动在硅胶管内循环流动，流速为40~60 mL/min；微藻溶液在微藻培养罐3中光照培养，由第2蠕动泵4带动在硅胶管内循环流动，流速为120~160 mL/min，透过空气泵5向微藻培养罐3中通入1L/L∙min 空气，沼液和微藻溶液在膜式光生物反应器6中汇合，沼液在中空纤维膜7管内循环流动，微藻溶液在中空纤维膜7管外循环流动，两者错流流动；沼液中超标氮、磷从中空纤维膜7内透过被膜外微藻溶液吸收，经过周期培养将沼液中超标氮、磷吸收，达到排放标准，当沼液储存罐1中沼液氮、磷吸收完时，无需更换微藻培养罐3中微藻，只在沼液储存罐1中需更换新沼液即可。
以下给出具体实施例。
实施例1
在用于处理沼液超标氮磷的膜式光生物反应器（membrane biophotoreactor, MPBR）中，首先将含高浓度氨氮的沼液浓度稀释为128 mg/L氨氮、26.2 mg/L磷酸盐。调配好的1000mL沼液加入沼液储存罐，在微藻培养罐里加入1000mL含有0.1g/L 名为C.sorokiniana 的微藻液体。整套装置放置于光照培养箱内，设置培养箱内的温度25 ℃，光照强度为7200 Lux。通过空气泵向微藻培养罐通入 1L/L∙min 的空气。蠕动泵以150~160 mL/min的循环流速带动微藻在膜外循环流动，使沼液在中空纤维膜内保持50~60 mL/min流速的循环流动。经过9天的培养，被处理的沼液氨氮下降到72.2 mg/L，磷酸盐下降到9.2 mg/L。
保持沼液浓度、微藻浓度、光照、温度，通气量等参数与上述相同，在普通光生物反应器(photobioreactor, PBR)中直接将微藻C.sorokiniana与沼液混合，处理其中的超标氮磷，经过9天的培养被处理的沼液氨氮下降到102.3 mg/L，磷酸盐下降到20.7 mg/L，处理沼液的速率明显下降。
膜式光生物反应器和普通光生物反应器中氨氮吸收的对比参见图2，膜式光生物反应器和普通光生物反应器中磷酸盐吸收的对比参见图 3。
实施例2
在膜式光生物反应器（membrane biophotoreactor, MPBR）中，首先将含高浓度氨氮的沼液浓度稀释为128 mg/L氨氮、26.2 mg/L磷酸盐。调配好的1000mL沼液加入沼液储存罐，在微藻培养罐里加入1000 mL含有0.1g/L 名为C.sorokiniana 的微藻液体。整套装置放置于光照培养箱内，设置培养箱内的温度为25 ℃，光照强度为7200 Lux。通过空气泵向微藻培养罐通入 1L/L∙min 的空气。蠕动泵以120~140 mL/min的循环流速带动微藻在膜外循环流动，使沼液在中空纤维膜内保持40~50 mL/min流速的循环流动。经过9天的第一批次培养第1天至第9天，被处理的沼液氨氮下降到72.2 mg/L，磷酸盐下降到9.2 mg/L。
保持沼液浓度、光照、温度，通气量、循环流速等参数与前一批相同，沼液储存罐中更换相同体积的沼液，而微藻培养罐中未加变动，继续第二批次培养第10天至于第18天。只经过9天的培养，被处理的沼液氨氮下降到51.4 mg/L，磷酸盐下降到2 mg/L，微藻处理沼液的速度明显得到高。
连续培养时膜式光生物反应器中前后批次氨氮吸收的对比参见图4，连续培养时膜式光生物反应器中前后批次磷酸盐吸收的对比参见图5。

Claims (10)

  1. 用于处理沼液超标氮磷的膜式光生物反应器，其特征在于设有沼液储存罐、 第1蠕动泵 、微藻培养罐、第2蠕动泵、空气泵、膜式光生物反应器和中空纤维膜；
    所述空气泵的出气口接微藻培养罐，中空纤维膜内嵌在膜式光生物反应器中，微藻培养罐的出口与膜式光生物反应器侧端两进出口连接，第2蠕动泵的进口接膜式光生物反应器的出口，第2蠕动泵的出口接微藻培养罐，微藻通过第2蠕动泵的带动在微藻培养罐和膜式光生物反应器之间循环流动，并且微藻处于膜式光生物反应器中的中空纤维膜外侧；沼液储存罐与膜式光生物反应器上下两端进出口连接，沼液通过第1蠕动泵的带动在沼液储存罐和膜式光生物反应器之间循环流动，并且沼液处于膜式光生物反应器中的中空纤维膜内侧。
  2. 如权利要求1所述用于处理沼液超标氮磷的膜式光生物反应器，其特征在于所述沼液储存罐通过直径为6mm的硅胶管与膜式光生物反应器上下两端进出口连接。
  3. 如权利要求1所述用于处理沼液超标氮磷的膜式光生物反应器，其特征在于所述微藻培养罐通过直径为6mm的硅胶管与膜式光生物反应器侧端两进出口连接。
  4. 如权利要求1所述用于处理沼液超标氮磷的膜式光生物反应器，其特征在于所述空气泵通过直径为6mm的硅胶管将空气压缩通入微藻培养罐。
  5. 如权利要求1所述用于处理沼液超标氮磷的膜式光生物反应器，其特征在于所述膜式光生物反应器为圆柱型光生物反应器，其高径比为6~7。
  6. 如权利要求1所述用于处理沼液超标氮磷的膜式光生物反应器，其特征在于所述中空纤维膜采用0.1μm中空纤维膜。
  7. 处理沼液中超标氮磷的方法，其特征在于采用如权利要求1~6中任一所述用于处理沼液超标氮磷的膜式光生物反应器，所述方法如下：
    含超标氮、磷的沼液贮存在沼液储存罐中，由第1蠕动泵带动在硅胶管内循环流动；微藻溶液在微藻培养罐中光照培养，由第2蠕动泵带动在硅胶管内循环流动，透过空气泵向微藻培养罐中通入空气，沼液和微藻溶液在膜式光生物反应器中汇合，沼液在中空纤维膜管内循环流动，微藻溶液在中空纤维膜管外循环流动，两者错流流动；沼液中超标氮、磷从中空纤维膜内透过被膜外微藻溶液吸收，经过周期培养将沼液中超标氮、磷吸收，达到排放标准，当沼液储存罐中沼液氮、磷吸收完时，无需更换微藻培养罐中微藻，只在沼液储存罐中需更换新沼液即可。
  8. 如权利要求7所述处理沼液中超标氮磷的方法，其特征在于所述沼液为秸秆、猪粪厌氧发酵产沼气后所产生的废液。
  9. 如权利要求7所述处理沼液中超标氮磷的方法，其特征在于所述由第1蠕动泵带动在硅胶管内循环流动的沼液循环流速为40~60 mL/min；所述由第2蠕动泵带动在硅胶管内循环流动的微藻溶液循环流速为120~160mL/min。
  10. 如权利要求7所述处理沼液中超标氮磷的方法，其特征在于所述通入空气的量为1L/L∙min 。
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