WO2020078433A1 - 酸性有机废水的处理及资源化利用方法 - Google Patents

酸性有机废水的处理及资源化利用方法 Download PDF

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WO2020078433A1
WO2020078433A1 PCT/CN2019/111721 CN2019111721W WO2020078433A1 WO 2020078433 A1 WO2020078433 A1 WO 2020078433A1 CN 2019111721 W CN2019111721 W CN 2019111721W WO 2020078433 A1 WO2020078433 A1 WO 2020078433A1
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activated sludge
treatment
microorganisms
microalgae
proteobacteria
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English (en)
French (fr)
Inventor
李海涛
毛松柏
汪东
陈曦
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Priority to JP2021546424A priority Critical patent/JP7466555B2/ja
Priority to US17/285,969 priority patent/US12060291B2/en
Publication of WO2020078433A1 publication Critical patent/WO2020078433A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • 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
    • C02F2209/22—O2
    • 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
    • C02F2303/04—Disinfection
    • 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
    • C02F2303/10—Energy recovery
    • 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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/341—Consortia of bacteria
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • 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
    • Y02E50/10—Biofuels, e.g. bio-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

Definitions

  • the invention belongs to the technical field of chemical industry, and in particular relates to a method for processing and resource utilization of acid organic wastewater.
  • CO 2 emission reduction is a major issue of climate change facing the world today. It is a serious challenge to the industrial economy, especially the energy industry. The emission reduction cost alone will have different effects on the social, economic, and technological development of countries at different stages of development.
  • the goal of the US Department of Energy is to gradually reduce the cost of CO 2 capture and storage (CCS) so that it does not exceed US $ 20 / t-CO 2 , or the cost of generating electricity does not increase by more than 20%.
  • Industrialized countries in the US and Europe are still striving for this, but even if this goal can be achieved, developing countries, including China, may not be able to afford it.
  • microalgae treats the wastewater
  • the remaining microalgae (“algal mud") is added to the thermal cracking link, and the microalgae is used as the raw material for the production of biomass gas.
  • chemical utilization The integration of wastewater treatment and energy production has high environmental protection significance and energy strategic significance.
  • CN201710938493.7 discloses a method for treating sewage by microalgae.
  • a hollow adsorption column assembled by using modified chitosan and modified montmorillonite as an adsorption membrane adsorbs metal ions in sewage, and the negative pressure is pumped.
  • the function allows sewage to pass through the adsorption column, the sewage stays in the adsorption column, and contacts the immobilized microalgae, and the microalgae use organic nutrients in the sewage to grow and reproduce.
  • Using this method for sewage treatment can effectively remove metal ions, carbon, nitrogen, phosphorus and other substances in sewage, and at the same time can cultivate microalgae on a large scale, achieving the dual purpose of sewage treatment and microalgae cultivation.
  • the treated sewage can be used for irrigation, breeding, cleaning, etc .; the cultivated microalgae can be used for aquaculture, feed addition, vegetable oil extraction, etc.
  • CN201610582744.8 discloses a microalgae optical biological sewage treatment device, which can use microalgae biofilm photosynthesis to generate hydrogen peroxide, and the hydrogen peroxide is converted into hydroxyl radicals by photochemical reaction under light conditions, which is very good Improve the microalgae sewage treatment effect.
  • CN201410731223.5 discloses a method for producing microalgae oil.
  • Microalgae culture medium and mixed microalgae seed liquid are added to a photobioreactor to maintain the pH of the culture system at 8-12, and the volume content of CO 2 in the gas is 5v% -45v%, improves the solubility and tolerance of the microalgae culture system to high concentration of CO 2 , improves the carbon fixation efficiency, the microalgae oil and fat harvest is obviously increased, and the production of biodiesel can be carried out.
  • CN201010222051.0 discloses an open-type method for cultivating microalgae, which uses an open-light bioreactor.
  • the open-light bioreactor includes microalgae and microalgae culture medium, and supplements CO 2 for the growth of microalgae.
  • the method of CO 2 is to use the gas-liquid mixing and conveying device to mix the gas containing CO 2 with the liquid phase, and then perform gas-liquid separation in the gas-liquid separator.
  • the liquid phase in which CO 2 is dissolved after the gas-liquid separation enters the open biological
  • the reactor supplements the CO 2 needed for the growth of microalgae.
  • CN105859034A discloses a high-COD, high-concentration organic hydrochloric acid organic chemical wastewater treatment method, which includes the following steps: S1, hydrogen peroxide and ferrous sulfate, Ca (OH) 2 and Na2CO3 are sequentially added to the wastewater, and the pH is adjusted by stirring Value is 6.5-8.5, after 1h at rest, the sediment is removed, and the organic chemical wastewater is discharged into the sedimentation tank; S2, molecular sieve is added to the wastewater in S1, stirred, after 1h at rest, the sediment is removed, and the supernatant is discharged into anaerobic reaction In the device; S3, maintaining the temperature of the supernatant in S2 at 15-35 °C, adding nitrogen and phosphorus sources according to the ratio of COD: N: P to 450: 5: 1, adjusting the pH value to 7.5-8.5, adding sulfate reducing bacteria The group undergoes anaerobic treatment, and is sent to the aerobic reactor after hydraulic retention for 24 hours; S4,
  • the first aspect of the present invention provides an acidic organic wastewater treatment and resource utilization method.
  • the method for treating and recycling acidic organic wastewater provided by the present invention includes the following steps:
  • step (2) The acidic organic wastewater treated in step (1) is treated with microalgae.
  • the present invention can significantly reduce the COD value of acidic organic wastewater by using a combination of activated sludge treatment and microalgae treatment.
  • the acidic organic wastewater is terephthalic acid wastewater.
  • the CODcr value of the acidic organic wastewater before treatment in step (1) is 3000-30000 mg / L.
  • the pH value of the acidic organic wastewater is 1-5.
  • the activated sludge is selected from aerobic activated sludge.
  • the activated sludge used in step (1) is activated sludge domesticated by activated sludge for municipal sewage treatment.
  • the activated sludge used for municipal sewage treatment cannot adapt to the acidic environment of wastewater. When it is used in the treatment of acidic organic wastewater, additional alkali needs to be added to adjust the pH to neutral, and the COD removal rate is low.
  • the microorganisms in the activated sludge for municipal sewage include Sphingobacteria (Sphingobacteriia) 20-25%, Beta-Proteobacteria (Betaproteobacteria) 20-25%, ⁇ -proteobacteria ( Gammaproteobacteria) 15-20% and Clostridia 10-15%. It is easily understood by those skilled in the art that in the context of the present invention, the above percentages related to the structure of microbial flora all refer to the abundance of bacteria, that is, the number of genes of a certain bacterium / total number of genes.
  • the microorganisms in the activated sludge for municipal sewage include 22.38% ⁇ 1% of Sphingobacteriia, 22.62% ⁇ 1% of ⁇ -proteobacteria, and ⁇ -proteobacteria (Gammaproteobacteria) 17.76% ⁇ 1% and Clostridia 11.57% ⁇ 1%.
  • the microorganisms in the activated sludge used in step (1) include Chlorobia whose content accounts for more than 10% of the total microorganisms, preferably more than 15%, more preferably 20-25% .
  • the microorganisms in the activated sludge used in step (1) include alpha-proteobacteria (Sphingobacteriia), beta-proteobacteria (Betaproteobacteria), and Chlorobia (Chlorobia) ), The total amount of which accounts for more than 50% of the total microorganisms, preferably more than 60%, and more preferably more than 70%. These four kinds of bacteria are dominant bacteria, and are the first four kinds of bacteria with the highest content in the microbial flora structure of the activated sludge used in step (1).
  • the microorganisms in the activated sludge used in step (1) include 15-25% of Alphaproteobacteria, 10-15% of Sphingobacteriia, 15-25 % Beta-Proteobacteria (Betaproteobacteria) and 20-25% of the green bacteria phylum, preferably 20-22% ⁇ -proteobacteria, 11-13% sphingolipids, 18-21% ⁇ -proteobacteria and 21-25% of Chlorobacteria.
  • the activated sludge in the above embodiment has the following advantages for the treatment of acidic organic wastewater: it has a strong adaptability to wastewater load fluctuations, and can self-adjust the pH value to a neutral state during the treatment process, so no additional treatment is required during the treatment process
  • the alkali adjusts the pH.
  • the sludge can be used continuously, and the activated sludge volume does not accumulate.
  • the microorganisms in the activated sludge used in step (1) include alpha-proteobacteria (Alphaproteobacteria) 35.90% ⁇ 1%, Sphingobacteriia (Sphingobacteriia) 23.83% ⁇ 1% and Deinococci ) 9.97% ⁇ 1%.
  • the microorganisms in the activated sludge used in step (1) include ⁇ -proteobacteria (Alphaproteobacteria) 21.59% ⁇ 1%, Sphingobacteriia (Sphingobacteriia) 12.68% ⁇ 1%, ⁇ -proteobacteria ( Betaproteobacteria) 19.15% ⁇ 1% and Chlorobia 23.26% ⁇ 1%.
  • the microorganisms in the activated sludge used in step (1) include Alphaproteobacteria, Sphingobacteriia and Deinococci.
  • the total amount of alpha-proteobacteria, Sphingobacteriia and Deinococci accounts for 50% of the total microorganisms
  • the above is preferably 60% or more, and more preferably 70% or more.
  • the microorganisms in the activated sludge used in step (1) include alpha-proteobacteria (Alphaproteobacteria) 30-40%, Sphingobacteria (Sphingobacteriia) 20-25% and Deinococci ) 8-12%.
  • the microorganisms in the activated sludge include alpha-proteobacteria (Alphaproteobacteria) 33-36%, Sphingobacteria (Sphingobacteriia) 22-24% and Deinococci 9-10 %.
  • the method for acclimating activated sludge includes:
  • the first stage of domestication the activated sludge used for the treatment of municipal sewage is cultivated for 8-10 days using acid wastewater with a CODcr value of 3000-5000mg / L and a pH value of 1-5.
  • the cultivation temperature of the first stage of domestication is 20-28 ° C, and the dissolved oxygen content is controlled at 1-5 mg / L.
  • the domestication method of activated sludge further includes a second stage of domestication after the first stage of domestication: the COD values are 6000-8000mg / L, 9000-15000mg / L, 16000 respectively -30000mg / L of acidic organic wastewater is used for cultivating the activated sludge acclimated in the first stage, and the cultivation time is 1-3 days.
  • the nitrogen source is provided by urea
  • the phosphorus source is provided by dipotassium hydrogen phosphate
  • the COD value represents the COD value of the wastewater used in the second stage of domestication
  • N and P are based on the element mass.
  • the cultivation temperature of the second stage of domestication is 20-28 ° C, and the dissolved oxygen amount is controlled at 2-4mg / L.
  • the activated sludge treatment time is 5-96h, preferably 5-48h. According to some preferred embodiments, the activated sludge treatment time is 2-6 hours, such as 3-5 hours.
  • the use of the activated sludge of the present invention for the treatment of acidic organic wastewater has the following advantages: it has a strong adaptability to wastewater load changes, and can self-adjust the pH value to a neutral state during the treatment process, so no additional alkali is required during the treatment process Adjust the pH.
  • the domesticated sludge can be used continuously, and the activated sludge volume does not accumulate.
  • the microalgae used in the microalgae treatment is Chlorella.
  • the microalgae are domesticated in the photobiological device before use.
  • the conditions for the microalgae acclimation treatment are preferably cultured with acidic organic wastewater to be treated for 10-16 days, while giving light, preferably with a light intensity of 3000-4100 lux.
  • the microalgae treatment time is 5-240h, preferably 12-36h. According to some preferred embodiments, the microalgae treatment time is 15-22 hours, such as 18-20 hours.
  • the method further includes performing ultraviolet light irradiation treatment on the acidic organic wastewater before the activated sludge treatment.
  • the treatment time of the ultraviolet light irradiation is 4-500 min, more preferably 5-60 min.
  • the method further includes using carbon dioxide from the industrial purge gas and / or biomass gas source as the carbon source for microalgae growth in the microalgae treatment.
  • the industrial purge gas is flue gas.
  • the content of carbon dioxide in the flue gas may be 8v% -15v%, preferably 10v% -12.5v%.
  • the carbon dioxide capture rate may be more than 90%.
  • the COD value of the acidic organic wastewater is less than 300 mg / L.
  • the method further includes: recovering the microalgae after the microalgae treatment is used, as a material of biomass energy for cracking to produce biomass fuel gas.
  • the present invention also provides a method for acclimating activated sludge, including:
  • the first stage of domestication the activated sludge used for the treatment of municipal sewage is cultivated for 8-10 days using acid wastewater with a COD value of 3000-5000mg / L and a pH value of 1-5.
  • the cultivation temperature of the first stage of domestication is 20-28 ° C.
  • the dissolved oxygen content is controlled at 2-4 mg / L.
  • the acclimation method further includes acclimation in the second stage after the first stage: using acidity with COD values of 6000-8000mg / L, 9000-15000mg / L, and 16000-30000mg / L respectively
  • the organic wastewater is used to cultivate the activated sludge acclimated in the first stage, and the cultivation time is 1-3 days.
  • the cultivation temperature of the second stage of domestication is 20-28 ° C, and the dissolved oxygen amount is controlled at 2-4mg / L.
  • the present invention also provides an activated sludge suitable for the treatment of acidic organic wastewater.
  • the microorganisms in the activated sludge include ⁇ -proteobacteria, Sphingobacteriia, ⁇ -deformation
  • the total amount of bacteria (Betaproteobacteria) and Chlorobia (Chlorobia) accounts for more than 50% of the total microorganisms, preferably more than 60%, more preferably more than 70%.
  • the microorganisms in the activated sludge include 15-25% Alphaproteobacteria, 10-15% Sphingobacteriia, 15-25% ⁇ -Proteobacteria (Betaproteobacteria) and 20-25% of the green bacteria phylum, preferably the microorganisms in the activated sludge include 20-22% of ⁇ -proteobacteria, 11-13% of sphingolipids, 18-21 % Beta-proteobacteria and 21-25% chlorobacteria.
  • the microorganisms in the activated sludge include alpha-proteobacteria (Sphingobacteriia), beta-proteobacteria (Betaproteobacteria), and Chlorobia (Chlorobia). More than 50% of the total microorganisms, preferably more than 60%, more preferably more than 70%.
  • the microorganisms in the activated sludge include 15-25% Alphaproteobacteria, 10-15% Sphingobacteriia, 15-25% ⁇ -proteobacteria (Betaproteobacteria) and 20-25% of the green phylum, preferably 20-22% of ⁇ -proteobacteria, 11-13% of sphingolipids, 18-21% of ⁇ -proteobacteria and 21-25% of green Fungi.
  • the microorganisms in the activated sludge include Chlorobia whose content accounts for more than 10% of the total microorganisms, preferably more than 15%, more preferably 20-25%.
  • the microorganisms in the activated sludge include Alphaproteobacteria, Sphingobacteriia and Deinococci.
  • the total amount of Alphaproteobacteria, Sphingobacteriia and Deinococci accounts for more than 50% of the total microorganisms, preferably more than 60%, more preferably 70% the above.
  • the microorganisms in the activated sludge include alpha-proteobacteria (Alphaproteobacteria) 30-40%, Sphingobacteria (Sphingobacteriia) 20-25% and Deinococci (Deinococci) 8-12 %.
  • the microorganisms in the activated sludge include alpha-proteobacteria (Alphaproteobacteria) 33-36%, Sphingobacteria (Sphingobacteriia) 22-24% and Deinococci 9-10 %.
  • the microorganisms in the activated sludge include alpha-proteobacteria (Alphaproteobacteria) 35.90% ⁇ 1%, Sphingobacteriia (Sphingobacteriia) 23.83% ⁇ 1% and Deinococci (Deinococci) 9.97% ⁇ 1% .
  • the microorganisms in the activated sludge include ⁇ -Proteobacteria (Alphaproteobacteria) 21.59% ⁇ 1%, Sphingobacteriia (Sphingobacteriia) 12.68% ⁇ 1%, ⁇ -Proteobacteria (Betaproteobacteria) 19.15% ⁇ 1 % And Chlorobia (Chlorobia) 23.26% ⁇ 1%.
  • the dominant bacteria of the microorganisms in the activated sludge are ⁇ -proteobacteria (Alphaproteobacteria) and Sphingobacteriia (Sphingobacteriia), ⁇ -proteobacteria (Betaproteobacteria) and Chlorobia (Chlorobia), respectively. 21-22%, 12-13%, 19-20% and 23-24%.
  • the dominant bacteria of the microorganisms in the activated sludge are ⁇ -proteobacteria (Alphaproteobacteria) and Sphingobacteriia (Sphingobacteriia), ⁇ -proteobacteria (Betaproteobacteria) and Chlorobia (Chlorobia)
  • the proportions are 21.59%, 12.68%, 19.15% and 23.26% respectively.
  • the activated sludge has the following advantages: it has a strong adaptability to acidic organic wastewater and wastewater load fluctuations, the activated sludge volume does not accumulate, and the pH value can be adjusted to a neutral state during the treatment process.
  • the present invention also provides the application of the activated sludge according to the second aspect and / or the third aspect of the present invention in the treatment of organic wastewater, especially acidic organic wastewater.
  • the acidic organic wastewater is terephthalic acid wastewater.
  • the pH value of the acidic organic wastewater is 1-5.
  • terephthalic acid wastewater refers to wastewater discharged during the production of terephthalic acid.
  • the main pollutants are terephthalic acid, acetic acid and benzoic acid.
  • the acidic organic wastewater treatment and resource utilization method provided by the present invention utilizes the technology of acidic organic wastewater treatment and flue gas carbon dioxide cultivation of microalgae, using CO 2 in flue gas and waste heat treatment of PTA wastewater, and simultaneously carrying out microalgal growth Material gasification, development of waste gas waste carbon dioxide industrial utilization technology, while purifying waste water, by-producing material energy, to achieve "waste waste” and "turn waste into treasure", in line with current green chemical and circular economy
  • the subject has great economic value and social significance.
  • the method of the invention solves the problem of low CO 2 utilization rate caused by the thin liquid layer in the existing open microalgae cultivation system, improves the capacity of the microalgae to accumulate oil during the microalgae cultivation process, improves the CO 2 utilization rate, and simplifies Cultivating device.
  • the activated sludge from the municipal sewage plant is taken and placed in an aerobic reaction device for domestication in the laboratory.
  • the entire domestication process is divided into two stages.
  • the activated sludge is cultivated with diluted terephthalic acid wastewater (COD concentration 3000-5000mg / L, pH value 4) for 8-10 days to obtain primary domesticated activated sludge;
  • the second stage (Deep domestication), use diluted terephthalic acid wastewater to further cultivate primary domesticated activated sludge for a total of 6-9 days.
  • the first 1-3 days were cultivated with COD 6000-8000mg / L diluted terephthalic acid wastewater; the fourth 4-6 days with COD 9000-15000mg / L diluted terephthalic acid wastewater; the 7-9 days COD is 16000-30000mg / L diluted terephthalic acid wastewater culture.
  • the acclimation culture temperature in the first and second stages is 20-28 °C, and the dissolved oxygen content is controlled at 2-4mg / L.
  • microorganisms in the activated sludge before domestication were mainly Sphingobacteriia (22.83%), ⁇ -proteobacteria (Betaproteobacteria, 22.62%), ⁇ -proteobacteria (Gammaproteobacteria, 17.76%) and Clostridia , 11.57%).
  • the microorganisms in the activated sludge after initial domestication were mainly alpha-proteobacteria (Alphaproteobacteria, 35.90%), Sphingobacteriia (23.83%) and Deinococci (9.97%). This result shows that the structure of the major flora has changed significantly.
  • Alphaproteobacteria and Sphingobacteriia are still the dominant bacteria, but the proportion has decreased from 35.90% and 23.83% at the initial domestication to 21.59% and 12.68%, respectively.
  • ⁇ -proteobacteria (Betaproteobacteria) and Chlorobia (Chlorobia) increased significantly, from 8.12% and 0.35% to 19.15% and 23.26%.
  • the Yobs value was 0.02-0.05g MLSS / g COD, in the domestication
  • the Yobs value in the second stage is 0.04-0.06g MLSS / g COD.
  • the acclimated activated sludge can raise the pH after the treatment of acid wastewater, which is the characteristic of the acclimated activated sludge of the present invention.
  • the activated sludge domesticated in the present invention has a strong adaptability to the fluctuation of PTA wastewater load, the volume of activated sludge does not accumulate, and the pH value can be self-adjusted to a neutral state during the treatment process.
  • Microalgae adopts Chlorella algae, a common species in freshwater, and is acclimated in a photobiological device in the laboratory. It is cultured for 10-16 days using the wastewater to be treated (terephthalic acid wastewater) at a culture temperature of 20-28 °C, while giving a certain amount of light every day, the light intensity is 3000-4100lux.
  • a sewage source containing PTA wastewater discharges 4 tons per day.
  • the CODcr content of PTA wastewater is 20000 mg / L
  • the water temperature is 40 ° C
  • the pH of the wastewater is 4.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, and then pretreatment of activated sludge (using the activated sludge after deep domestication described above) is performed.
  • the pH value of the wastewater after sludge treatment is 5.8, and the CODcr content is 1809 mg / L. After that, the water sample enters the microalgae pond for microalgae (Chlorella genus) treatment.
  • the flue gas with a carbon dioxide content of 12v% is supplied to supply carbon dioxide for the production of microalgae.
  • a total treatment residence time of 24h including ultraviolet irradiation treatment for 10min, Activated sludge treatment 8h, microalgae treatment 15.83h
  • PTA wastewater CODcr content is 128mg / L
  • the capture rate of carbon dioxide in flue gas reaches 91%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • PTA-containing wastewater and flue gas conditions are the same as in Example 1, except that the traditional activated sludge process is adopted, in which the above activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is 4, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA. It can only be treated by neutralization and dilution. The treatment cycle is 48 hours, and the CODcr content of the treated wastewater is 1000 mg / L.
  • a sewage source containing PTA wastewater discharges 40 tons per day.
  • the CODcr content of PTA wastewater is 15000 mg / L
  • the water temperature is 40 ° C
  • the pH of the wastewater is 4.4.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, then activated sludge pretreatment, and then the water sample enters the microalgae pond for microalgae treatment.
  • the flue gas with a carbon dioxide content of 8v% is supplied with carbon dioxide for the production of microalgae.
  • the CODcr content of PTA wastewater is 107mg / L
  • the capture rate of carbon dioxide in flue gas reaches 90.8%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the conditions of wastewater and flue gas containing PTA are the same as in Example 2, except that the traditional activated sludge method is adopted, and the traditional activated sludge method is adopted. After the wastewater to be treated is fully mixed, aerate. Because the pH value of the wastewater is 4.4, the active components in the sludge are difficult to survive. The traditional method cannot treat wastewater containing PTA. It can only be treated by neutralization and dilution. The treatment cycle is 48 hours, and the CODcr content of the treated wastewater is 1000 mg / L.
  • a sewage source containing PTA wastewater discharges 10 tons per day.
  • the CODcr content of PTA wastewater is 30,000 mg / L, the water temperature is 45 ° C, and the pH of the wastewater is 3.8.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, and then activated sludge pretreatment is performed.
  • the pH value of the wastewater after activated sludge treatment is 6.1.
  • the CODcr content is 2910mg / L.
  • the water sample enters the microalgae pond for microalgae treatment, and at the same time, the flue gas with a carbon dioxide content of 15v% is supplied to supply carbon dioxide for the microalgae production.
  • the CODcr content of PTA wastewater is 159mg / L
  • the capture rate of carbon dioxide in flue gas reaches 91.5%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the wastewater and flue gas conditions containing PTA are the same as in Example 3, except that the traditional activated sludge process is adopted, in which the activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is 3.8, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA. It can only be treated by neutralization and dilution. The treatment cycle is 60 hours, and the CODcr content of the treated wastewater is 1200 mg / L.
  • a sewage source containing PTA wastewater discharges 1 ton per day.
  • the CODcr content of PTA wastewater is 10000mg / L, the water temperature is 35 °C, and the pH value of the wastewater is 4.8.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, and then activated sludge pretreatment is performed. The pH value of the wastewater after activated sludge treatment is 5.98.
  • the CODcr content is 1851mg / L.
  • the water sample enters the microalgae pond for microalgae treatment, and at the same time, the flue gas with a carbon dioxide content of 12v% is supplied to supply carbon dioxide for the microalgae production.
  • Microalgae treatment 12.93h) the CODcr content of PTA wastewater is 89mg / L, and the capture rate of carbon dioxide in flue gas reaches 93.5%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the wastewater and flue gas conditions containing PTA are the same as in Example 4, except that the traditional activated sludge process is adopted, in which the activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is 4.8, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA, and can only be treated by neutralization and dilution.
  • the treatment cycle is 40 hours, and the CODcr content of the treated wastewater is 700 mg / L.
  • a sewage source containing PTA wastewater discharges 80 tons per day.
  • the CODcr content of PTA wastewater is 17000 mg / L, the water temperature is 45 ° C, and the pH of the wastewater is 4.5.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet irradiation to decompose PTA molecules, and then activated sludge pretreatment is performed.
  • the pH value of the wastewater after activated sludge treatment is 6.02.
  • the CODcr content is 2080mg / L.
  • the water sample enters the microalgae pond for microalgae treatment, and at the same time, the flue gas with a carbon dioxide content of 10v% is supplied to supply carbon dioxide for the production of microalgae.
  • the CODcr content of PTA wastewater is 129mg / L
  • the capture rate of carbon dioxide in flue gas reaches 90.5%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • PTA-containing wastewater and flue gas conditions are the same as in Example 5, except that the traditional activated sludge process is used, in which the above activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is 4.5, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA. It can only be treated by neutralization and dilution. The treatment cycle is 36 hours.
  • the CODcr content of the treated wastewater is 1300 mg / L.
  • a sewage source containing PTA wastewater discharges 30 tons per day.
  • the CODcr content of PTA wastewater is 23000 mg / L
  • the water temperature is 40 ° C
  • the pH of the wastewater is 4.2.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, and then activated sludge pretreatment is performed.
  • the pH value of the wastewater after activated sludge treatment is 5.95.
  • the CODcr content is 4810mg / L.
  • the water sample enters the microalgae pond for microalgae treatment, and at the same time, the flue gas with a carbon dioxide content of 12.5% is supplied to supply carbon dioxide for the production of microalgae.
  • the CODcr content of PTA wastewater is 179mg / L
  • the capture rate of carbon dioxide in flue gas reaches 91.3%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • PTA-containing wastewater and flue gas conditions are the same as in Example 6, except that the traditional activated sludge process is adopted, in which the activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is 4.2, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA. It can only be treated by neutralization and dilution. The treatment cycle is 42 hours.
  • the CODcr content of the treated wastewater is 1500 mg / L.
  • a sewage source containing PTA wastewater discharges 15 tons per day.
  • the CODcr content of PTA wastewater is 29000 mg / L
  • the water temperature is 40 ° C
  • the pH of the wastewater is 3.9.
  • the method provided by the present invention is used for treatment. First, ultraviolet light with a wavelength of 365 nm is used for ultraviolet light irradiation to decompose PTA molecules, and then activated sludge pretreatment is performed.
  • the pH value of the wastewater after activated sludge treatment is 5.89.
  • the CODcr content is 3284mg / L. After that, the water sample enters the microalgae pond for microalgae treatment.
  • the flue gas with a carbon dioxide content of 12v% is supplied to supply carbon dioxide for the production of microalgae.
  • PTA wastewater CODcr content is 209mg / L
  • the capture rate of carbon dioxide in flue gas reached 90.3%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the wastewater and flue gas conditions containing PTA are the same as in Example 7, except that the traditional activated sludge process is adopted, in which the activated sludge from the municipal sewage plant will be fully mixed with the wastewater to be treated, and then exposed gas. Because the pH value of the wastewater is about 3.9, the active components in the sludge are difficult to survive.
  • the traditional method cannot treat wastewater containing PTA, and can only be treated by neutralization and dilution.
  • the treatment cycle is 45h, and the CODcr content of the treated wastewater is 1700mg / L.
  • Example 1 The wastewater and treatment steps used in Example 1 are basically the same, the only difference is that the activated sludge used in the activated sludge pretreatment step is the non-domesticated activated sludge, that is, the activated sludge from the municipal sewage plant.
  • the activated sludge used in the activated sludge pretreatment step is the non-domesticated activated sludge, that is, the activated sludge from the municipal sewage plant.
  • the CODcr content of the treated PTA wastewater is 11000mg / L, and the capture rate of carbon dioxide in flue gas reaches 5%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • Example 1 The wastewater and treatment steps used in Example 1 are basically the same, the only difference is that the activated sludge after the preliminary domestication is used in the activated sludge pretreatment step.
  • the CODcr content of the treated PTA wastewater is 450mg / L, and the capture rate of carbon dioxide in flue gas reaches 71%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the difference in the treatment steps is that the ultraviolet light with a wavelength of 365 nm is not used to irradiate the wastewater with ultraviolet light. That is, wastewater is treated in two steps: activated sludge (8 hours) and microalgae (16 hours).
  • the CODcr content of the treated PTA wastewater is 780mg / L, and the capture rate of carbon dioxide in flue gas reaches 85%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • the difference in the treatment steps is only that the microalgae treatment is not used, that is, the wastewater is irradiated with ultraviolet light and activated sludge, in which ultraviolet light is irradiated for 10 minutes and activated sludge is treated for 23 hours and 50 minutes .
  • the CODcr content of the treated PTA wastewater is 124 mg / L, and the capture rate of carbon dioxide in flue gas is 0%.
  • the treatment step is different in the microalgae treatment step, the type of microalgae used is different, in this example the microalgae is Microcystis (Microcystis).
  • the CODcr content of the treated PTA wastewater is 205mg / L, and the capture rate of carbon dioxide in flue gas reaches 70%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • Example 1 The difference from Example 1 is that the ultraviolet irradiation time is extended to 80 minutes, the activated sludge treatment time is 8 hours, and the microalgae treatment time is 15.5 hours.
  • the CODcr content of the treated PTA wastewater is 135mg / L, and the capture rate of carbon dioxide in flue gas reaches 91.2%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • Example 1 The difference from Example 1 is that the ultraviolet irradiation time is 10 minutes, the activated sludge treatment time is 4 hours, and the microalgae treatment time is 19 hours and 50 minutes.
  • the CODcr content of the treated PTA wastewater is 92mg / L, and the capture rate of carbon dioxide in flue gas reaches 95.4%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.
  • Example 1 The difference from Example 1 is that the ultraviolet irradiation time is 10 minutes, the activated sludge treatment time is 11 hours and 55 minutes, and the microalgae treatment time is 11 hours and 55 minutes.
  • the CODcr content of the treated PTA wastewater is 112mg / L, and the capture rate of carbon dioxide in flue gas reaches 93.2%.
  • the microalgae in the reactor are regularly replaced and used to crack the fuel gas.

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Abstract

本发明公开了一种酸性有机废水的处理及资源化利用方法，包括(1)将酸性有机废水进行活性污泥处理；(2)将步骤(1)处理后的酸性有机废水进行微藻处理。本发明通过采用活性污泥处理和微藻处理的组合可以显著降低酸性有机废水的COD。在一些实施方式中，通过使用驯化后的活性污泥或特定微生物菌群结构的活性污泥不仅可以提高处理效率，缩短处理时间，还能省去调节pH值的步骤，同时不会造成污泥累积。

Description

酸性有机废水的处理及资源化利用方法
相关申请
本申请要求享有2018年10月18日提交的申请号为201811215345.3，发明名称为“一种对苯二甲酸废水处理及资源化利用方法”的中国专利申请的优先权，其内容通过结合并入本文。
技术领域
本发明属于化工技术领域，具体涉及一种酸性有机废水的处理及资源化利用方法。
背景技术
CO 2减排是当今全球面临的气候变化重大问题，对工业经济尤其能源产业是严峻挑战，单就减排成本而论对不同发展阶段的国家社会、经济、科技发展会有不相同的影响。美国能源部的目标是逐步降低CO 2捕集与封存(CCS)的成本使其不超过20美元/t-CO 2、或发电成本增加不超过20％。美、欧工业化国家至今仍在为之努力，但即使能达到这一目标，包括中国在内的发展中国家未必负担得起。
随着国民经济的不断发展，对石油化工的需求量也不断增多，随之而来的废水排放问题越来越大，情况越来越复杂。生物法水处理技术作为一种绿色化工技术，具有处理废水彻底、处理成本低、药剂消耗少和无二次污染等特点，已经成为当前污水处理的主流技术。作为新型水处理技术，微藻具有生长速率快、收获时期短、光合利用效率高等特点，在生长繁殖过程中能将水体中的有机化合物作为氮源及硫源来富积吸收与利用，也能在以CO 2作为无机碳源的同时利用有机物质作为有机碳源。在微藻处理废水之后，加入剩余微藻(“藻泥”)热裂解环节，将微藻作为制取生物质气的原材料，在避免微藻对环境带来二次污染风险的同时，实现资源化利用。废水处理环节与能源生产环节的集成，具有较高的环境保护意义与能源战略意义。
CN201710938493.7公开了一种微藻处理污水的方法，利用改性壳聚糖、改性蒙脱石制备成吸附膜组装而成的中空吸附柱对污水中的金属离子进行吸附，通过泵负压作用使污水透过吸附柱，污水在吸附柱中停留，与固定化微藻接触，微藻利用污水中的有机营养物质进行生长繁殖。利用该方法进行污水处理，能有效的除去污水中的金属离子、碳、氮、 磷等物质，同时能大规模培养微藻，达到污水处理与微藻培养双重目的。处理后的污水可用于灌溉、养殖、清洗等；培养出来的微藻可用于水产养殖、饲料添加、植物油提取等。
CN201610582744.8公开了一种微藻光学生物污水处理装置，其可以利用微藻生物膜光合作用可以生成过氧化氢，并且过氧化氢在光照条件下通过光化学反应转化成羟基自由基，很好的提高了微藻污水处理效果。CN201410731223.5公开了一种生产微藻油脂的方法，在光生物反应器中加入微藻培养基和混合微藻种子液，维持培养体系pH为8-12，通入气体中CO 2体积含量为5v％-45v％，提高了微藻培养体系对高浓度CO 2的溶解性和耐受性，提高了固碳效率，微藻油脂的收获量明显提高，能够进行生物柴油的生产。
CN201010222051.0公开了一种敞开式培养微藻的方法，采用光照敞开式生物反应器，光照敞开式生物反应器内包括微藻和微藻培养基，补充CO 2用于微藻生长，其中补充CO 2的方法为利用气液混合输送装置将含CO 2的气体与液相混合，然后在气液分离器中进行气液分离，气液分离后的溶有CO 2的液相进入敞开式生物反应器补充微藻生长所需的CO 2。
CN105859034A公开了一种高COD、高浓度有机盐酸性有机化工废水处理方法，其包括如下步骤：S1、往废水中依次添加过氧化氢和硫酸亚铁，Ca(OH)2以及Na2CO3，搅拌调节pH值至6.5-8.5，静止1h后去除沉淀，将有机化工废水排入沉淀池中；S2、向S1中的废水里加入分子筛，搅拌，静止1h后去除沉淀，将上清液排入厌氧反应器中；S3、维持S2中上清液温度为15-35℃，按照COD:N:P为450:5:1的比例添加氮磷源，调节pH值为7.5-8.5，加入硫酸盐还原菌群进行厌氧处理，水力停留24h后输送至好氧反应器中；S4、维持S3中上清液温度为20-35℃，按照COD:N:P为250:5:1的比例添加氮磷源，调节pH值为6.5-8，添加嗜盐菌群和耐盐菌群进行一段好氧处理，曝气搅拌，水力停留24h后经二段好氧处理，曝气搅拌，水力停留24h；S5、沉淀并上清出水。该废水处理工艺复杂，耗时长、需要调节pH，有大量碱液消耗。
发明内容
针对现有技术的不足，本发明第一个方面提供一种酸性有机废水的处理及资源化利用方法。
本发明提供的酸性有机废水的处理及资源化利用方法包括以下步骤：
(1)将酸性有机废水进行活性污泥处理；
(2)将步骤(1)处理后的酸性有机废水进行微藻处理。
本发明通过采用活性污泥处理和微藻处理的组合可以显著降低酸性有机废水的COD 值。
根据本发明的一些实施方式，所述酸性有机废水为对苯二甲酸废水。
根据本发明的一些实施方式，步骤(1)处理之前酸性有机废水的CODcr值为3000-30000mg/L。
根据本发明的一些实施方式，所述酸性有机废水的pH值为1-5。
在一些实施方式中，所述活性污泥选自好氧活性污泥。
根据本发明的一些实施方式，步骤(1)中使用的活性污泥为将处理市政污水用的活性污泥驯化后的活性污泥。市政污水处理用的活性污泥无法适应废水的酸性环境，在用于酸性有机废水处理时，需要额外加碱调节pH至中性，并且COD去除率低。
根据本发明的一些实施方式，所述市政污水用的活性污泥中的微生物包括鞘脂杆菌纲(Sphingobacteriia)20-25％、β-变形菌(Betaproteobacteria)20-25％，γ-变形菌(Gammaproteobacteria)15-20％和梭状芽胞杆菌(Clostridia)10-15％。本领域技术人员容易理解，本发明上下文中，涉及微生物菌群结构的以上百分比均指细菌丰度，即某菌的基因数/总基因数。
在一个具体实施例中，所述市政污水用的活性污泥中的微生物包括鞘脂杆菌纲(Sphingobacteriia)22.83％±1％、β-变形菌(Betaproteobacteria)22.62％±1％，γ-变形菌(Gammaproteobacteria)17.76％±1％和梭状芽胞杆菌(Clostridia)11.57％±1％。
根据本发明的一些实施方式，步骤(1)使用的所述活性污泥中的微生物包括含量占总微生物的10％以上，优选15％以上，更优选20-25％的绿菌纲(Chlorobia)。
根据本发明的一些实施方式，步骤(1)使用的活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)、鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌纲(Chlorobia)，其总量占总微生物的50％以上，优选60％以上，更优选70％以上。这四种菌为优势菌，是步骤(1)使用的活性污泥中的微生物的菌群结构中含量最高的前四种菌。
根据本发明的一些实施方式，步骤(1)使用的活性污泥中的微生物包括15-25％的α-变形菌(Alphaproteobacteria)、10-15％的鞘脂杆菌纲(Sphingobacteriia)、15-25％的β-变形菌(Betaproteobacteria)和20-25％的绿菌门，优选20-22％的α-变形菌，11-13％的鞘脂杆菌纲，18-21％的β-变形菌以及21-25％的绿菌纲。
上述实施方式中的活性污泥用于处理酸性有机废水具有以下优势：对废水负荷变动有很强的适应性，可以在处理过程中自我调节pH值至中性状态，因此处理过程中无需额外加碱调节pH。此外，污泥可以持续使用，活性污泥体积不累积。
根据一些具体实施例，步骤(1)使用的活性污泥中的微生物包括α-变形菌 (Alphaproteobacteria)35.90％±1％，鞘脂杆菌纲(Sphingobacteriia)23.83％±1％和异常球菌纲(Deinococci)9.97％±1％。
根据一些具体实施例，步骤(1)使用的活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)21.59％±1％、鞘脂杆菌纲(Sphingobacteriia)12.68％±1％，β-变形菌(Betaproteobacteria)19.15％±1％和绿菌纲(Chlorobia)23.26％±1％。
根据本发明的一些实施方式，步骤(1)使用的所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)。
根据本发明的一些实施方式，步骤(1)使用的活性污泥中，α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)的总量占总微生物的50％以上，优选60％以上，更优选70％以上。
根据本发明的一些实施方式，步骤(1)使用的活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)30-40％，鞘脂杆菌纲(Sphingobacteriia)20-25％和异常球菌纲(Deinococci)8-12％。
根据本发明的一些实施方式，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)33-36％，鞘脂杆菌纲(Sphingobacteriia)22-24％和异常球菌纲(Deinococci)9-10％。
根据本发明的一些优选实施方式，所述活性污泥的驯化方法包括：
第一阶段驯化：将处理市政污水用的活性污泥采用CODcr值为3000-5000mg/L，pH值为1-5的酸性废水培养8-10天。
优选地，第一阶段驯化的培养温度均为20-28℃，溶氧量控制在1-5mg/L。
根据本发明的一些更优选实施方式，所述活性污泥的驯化方法还包括在第一阶段驯化之后的第二阶段驯化：用COD值分别为6000-8000mg/L、9000-15000mg/L、16000-30000mg/L的酸性有机废水依次对第一阶段驯化后的活性污泥进行培养，培养时间均为1-3天。优选地，在第二阶段驯化过程中，添加N和P营养物质，氮源由尿素提供，磷源由磷酸氢二钾提供，比例为COD值：N：P＝(95-102)：(0.8-1.3)：(0.7-1.2)，COD值表示第二阶段驯化使用的废水的COD值，N和P以元素质量计。
优选地，第二阶段驯化的培养温度均为20-28℃，溶氧量控制在2-4mg/L。
根据本发明的一些实施方式，所述活性污泥处理的时间为5-96h，优选为5-48h。根据一些优选实施例，所述活性污泥处理的时间为2-6小时，如3-5小时。
使用本发明的活性污泥用于处理酸性有机废水具有以下优势：对废水负荷变动有很强的适应性，可以在处理过程中自我调节pH值至中性状态，因此处理过程中无需额外加碱 调节pH。此外，驯化后的污泥可以持续使用，活性污泥体积不累积。
而采用普通活性污泥如市政污水处理用的活性污泥由于无法适应废水的酸性环境，需要额外加碱调节pH至中性，COD去除率低。
根据本发明的一些实施方式，所述微藻处理中使用的微藻为小球藻属。优选地，在使用前在光生物装置中将微藻驯化处理。微藻驯化处理的条件优选为使用待处理酸性有机废水培养10-16天，同时给予光照，优选光照强度为3000-4100lux。
根据本发明的一些实施方式，所述微藻处理的时间为5-240h，优选为12-36h。根据一些优选实施例，所述微藻处理的时间为15-22小时，如18-20小时。
根据本发明的一些实施方式，所述方法还包括在活性污泥处理之前对酸性有机废水进行紫外光照射处理。优选地，所述紫外光照射处理的时间为4-500min，更优选为5-60min。
根据本发明的一些实施方式，所述方法还包括在所述微藻处理中，采用工业驰放气和/或生物质气源中的二氧化碳作为微藻生长的碳源。优选地，所述工业驰放气为烟气。所述烟气中二氧化碳的含量可以为8v％-15v％，优选为10v％-12.5v％。所述微藻处理过程中，所述二氧化碳的捕集率可以为90％以上。
根据本发明的一些实施方式，经微藻处理后，所述酸性有机废水的COD值为小于300mg/L。
根据本发明的一些实施方式，所述方法还包括：将微藻处理使用后的微藻回收，作为生物质能源的材料用于裂解制生物质燃料气。
第二方面，本发明还提供了一种活性污泥的驯化方法，包括：
第一阶段驯化：将处理市政污水用的活性污泥采用COD值为3000-5000mg/L，pH值为1-5的酸性废水培养8-10天。
优选地，第一阶段驯化的培养温度均为20-28℃，溶氧量控制在2-4mg/L。
根据本发明的一些优选实施方式，所述驯化方法还包括在第一阶段之后的第二阶段驯化：用COD值分别为6000-8000mg/L、9000-15000mg/L、16000-30000mg/L的酸性有机废水依次对第一阶段驯化后的活性污泥进行培养，培养时间均为1-3天。优选地，在第二阶段驯化过程中，添加N和P营养物质，氮源由尿素提供，磷源由磷酸氢二钾提供，比例为COD：N：P＝(95-102)：(0.8-1.3)：(0.7-1.2)，COD表示第二阶段驯化使用的废水的COD值，N和P以元素质量计。
优选地，第二阶段驯化的培养温度均为20-28℃，溶氧量控制在2-4mg/L。
第三方面，本发明还提供了一种适用于处理酸性有机废水的活性污泥，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)、鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌纲(Chlorobia)，其总量占总微生物的50％以上，优选60％以上，更优选70％以上。
根据本发明的一些实施方式，所述活性污泥中的微生物中包括15-25％的α-变形菌(Alphaproteobacteria)、10-15％的鞘脂杆菌纲(Sphingobacteriia)、15-25％的β-变形菌(Betaproteobacteria)和20-25％的绿菌门，优选所述活性污泥中的微生物中包括20-22％的α-变形菌，11-13％的鞘脂杆菌纲，18-21％的β-变形菌以及21-25％的绿菌纲。
根据本发明的一些实施方式，活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)、鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌纲(Chlorobia)，其总量占总微生物的50％以上，优选60％以上，更优选70％以上。
根据本发明的一些实施方式，活性污泥中的微生物包括15-25％的α-变形菌(Alphaproteobacteria)、10-15％的鞘脂杆菌纲(Sphingobacteriia)、15-25％的β-变形菌(Betaproteobacteria)和20-25％的绿菌门，优选20-22％的α-变形菌，11-13％的鞘脂杆菌纲，18-21％的β-变形菌以及21-25％的绿菌纲。
根据本发明的一些实施方式，所述活性污泥中的微生物包括含量占总微生物的10％以上，优选15％以上，更优选20-25％的绿菌纲(Chlorobia)。
根据本发明的一些实施方式，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)。
根据本发明的一些实施方式，α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)的总量占总微生物的50％以上，优选60％以上，更优选70％以上。
根据本发明的一些实施方式，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)30-40％，鞘脂杆菌纲(Sphingobacteriia)20-25％和异常球菌纲(Deinococci)8-12％。
根据本发明的一些实施方式，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)33-36％，鞘脂杆菌纲(Sphingobacteriia)22-24％和异常球菌纲(Deinococci)9-10％。根据一些具体实施例，活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)35.90％±1％，鞘脂杆菌纲(Sphingobacteriia)23.83％±1％和异常球菌纲(Deinococci)9.97％±1％。
根据一些具体实施例，活性污泥中的微生物包括α-变形菌 (Alphaproteobacteria)21.59％±1％、鞘脂杆菌纲(Sphingobacteriia)12.68％±1％，β-变形菌(Betaproteobacteria)19.15％±1％和绿菌纲(Chlorobia)23.26％±1％。
根据一些优选实施例，活性污泥中的微生物的优势菌为α-变形菌(Alphaproteobacteria)和鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌门(Chlorobia)，比例分别为21-22％、12-13％、19-20％和23-24％。更具体地，在一些实施例中，活性污泥中的微生物的优势菌为α-变形菌(Alphaproteobacteria)和鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌门(Chlorobia)，其比例分别21.59％、12.68％、19.15％和23.26％。
在上述实施方式中，所述活性污泥具有以下优势：对酸性有机废水废水负荷变动有很强的适应性，活性污泥体积不累积，可以在处理过程中自我调节pH值至中性状态。
第四个方面，本发明还提供了根据本发明第二个方面和/或第三个方面所述的活性污泥在有机废水处理中的应用，尤其是酸性有机废水。在一些实施例中，所述酸性有机废水为对苯二甲酸废水。在一些实施例中，所述酸性有机废水的pH值为1-5。
本申请中，术语“对苯二甲酸废水”是指对苯二甲酸生产过程中排放的废水，主要污染物为对苯二甲酸、醋酸和苯甲酸等。
根据一些实施方式，本发明提供的酸性有机废水处理及资源化利用方法通过酸性有机废水处理和烟气二氧化碳培养微藻技术，利用烟气中的CO 2和余热处理PTA废水，同时进行微藻生物质气化，开发以废制废的烟气二氧化碳工业利用技术，在净化废水的同时副产生物质能源，实现“以废制废”和“变废为宝”，符合当前绿色化工和循环经济的主体，具有巨大的经济价值和社会意义。此外，本发明方法解决了现有敞开式微藻培养体系中由于液层薄引起的CO 2利用率低的问题，提高了微藻培养过程中微藻积累油脂能力，提高了CO 2利用率，简化了培养装置。
具体实施方式
为使本发明的技术方案更加容易理解，下面将结合实施例来详细说明本发明，这些实施例仅起说明性作用，并不局限于本发明的应用范围。
一、活性污泥
1、微生物驯化过程
取来自市政污水厂的活性污泥，在实验室置于好氧反应装置中驯化处理，整个驯化过程分为两阶段。第一阶段(初步驯化)，用稀释的对苯二甲酸废水(COD浓度为3000-5000mg/L，pH值为4)培养活性污泥8-10天，得到初级驯化活性污泥；第二阶段(深度驯化)，使用稀释的对苯二甲酸废水进一步培养初级驯化活性污泥共计6-9天。其中，第1-3天用COD为6000-8000mg/L稀释对苯二甲酸废水培养；第4-6天用COD为9000-15000mg/L稀释对苯二甲酸废水培养；第7-9天用COD为16000-30000mg/L稀释对苯二甲酸废水培养。在深度驯化过程中，添加N和P营养物质，氮源由尿素提供，磷源由磷酸氢二钾提供，比例为COD：N:P＝95-102：0.8-1.3：0.7-1.2。第一与第二阶段驯化培养温度均为20-28℃，溶氧量控制在2-4mg/L。
2、微生物菌群结构解析与表征
测活性污泥中各微生物的种类及含量：活性污泥样品收集，DNA抽提和PCR扩增，Illumina Miseq测序，得到测序结果分析确定种类与含量(丰度)。
未驯化前活性污泥中的微生物主要为鞘脂杆菌纲(Sphingobacteriia,22.83％)、β-变形菌(Betaproteobacteria,22.62％)，γ-变形菌(Gammaproteobacteria,17.76％)和梭状芽胞杆菌(Clostridia,11.57％)。
初步驯化之后的活性污泥中的微生物主要以α-变形菌(Alphaproteobacteria,35.90％)，鞘脂杆菌纲(Sphingobacteriia,23.83％)和异常球菌纲(Deinococci,9.97％)为主。该结果显示主要菌群结构发生了较大的改变。
通过深度驯化后，α-变形菌(Alphaproteobacteria)和鞘脂杆菌纲(Sphingobacteriia)还是优势菌纲，但是所占比例由初步驯化时候的35.90％和23.83％分别下降到了21.59％和12.68％。此外β-变形菌(Betaproteobacteria)和绿菌门(Chlorobia)有明显增加，由8.12％和0.35％增加到了19.15％和23.26％。
检测了活性污泥表观产率Yobs值(Yobs＝污泥增长量/COD消耗量(mg MLSS/mg COD)。在驯化第一阶段Yobs值为0.02-0.05g MLSS/g COD，在驯化第二阶段Yobs值为0.04-0.06g MLSS/g COD。这表明经过初步驯化和深度驯化后，活性污泥中的微生物的群落结构优化，达到了适应性生长与内源性消耗的动态平衡，因此，活性污泥不产生积累。
此外，驯化后的活性污泥能够在酸性废水处理后使pH回升，这是本发明驯化后的活性污泥的特性。
总之，本发明驯化的活性污泥对PTA废水负荷变动有很强的适应性，活性污泥体积 不累积，可以在处理过程中自我调节pH值至中性状态。
二、微藻
微藻采用淡水中的常见种类小球藻属(Chlorella)藻种，在实验室置于光生物装置中驯化处理，使用待处理废水(对苯二甲酸废水)培养10-16天，培养温度为20-28℃，同时每天给予一定的光照，光照强度为3000-4100lux。
实施例1
一个含有PTA废水的污水源每天排放量4吨，PTA废水的CODcr含量为20000mg/L，水温40℃，废水的pH值为4。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥(采用上述深度驯化后的活性污泥)预处理，活性污泥处理后的废水的pH值为5.8，CODcr含量为1809mg/L。之后水样进入微藻池进行微藻(小球藻属)处理，同时通入二氧化碳含量为12v％的烟气为微藻生产供应二氧化碳，总共处理停留时间24h后(其中紫外光照射处理10min，活性污泥处理8h，微藻处理15.83h)，PTA废水的CODcr含量为128mg/L，烟气中二氧化碳的捕集率达到91％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例1
含PTA的废水和烟气条件与实施例1相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为4，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期48h，处理后废水的CODcr含量为1000mg/L。
实施例2
一个含有PTA废水的污水源每天排放量40吨，PTA废水的CODcr含量为15000mg/L，水温40℃，废水的pH值为4.4。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为8v％的烟气为微藻生产供应二氧化碳，总共处理停留时间20h后(其中紫外光照射处理15min，活性污泥处理6.75h，微藻处理13h)，PTA废水的CODcr含量为107mg/L，烟气中二氧化碳的捕集率达到90.8％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例2
含PTA的废水和烟气条件与实施例2相同，不同之处在于，采用传统的活性污泥法处理，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为4.4，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期48h，处理后废水的CODcr含量为1000mg/L。
实施例3
一个含有PTA废水的污水源每天排放量10吨，PTA废水的CODcr含量为30000mg/L，水温45℃，废水的pH值为3.8。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，活性污泥处理后的废水的pH值为6.1，CODcr含量为2910mg/L。之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为15v％的烟气为微藻生产供应二氧化碳，总共处理停留时间28h后(其中紫外光照射处理6min，活性污泥处理13h，微藻处理14.9h)，PTA废水的CODcr含量为159mg/L，烟气中二氧化碳的捕集率达到91.5％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例3
含PTA的废水和烟气条件与实施例3相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为3.8，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期60h，处理后废水的CODcr含量为1200mg/L。
实施例4
一个含有PTA废水的污水源每天排放量1吨，PTA废水的CODcr含量为10000mg/L，水温35℃，废水的pH值为4.8。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，活性污泥处理后的废水的pH值为5.98，CODcr含量为1851mg/L。之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为12v％的烟气为微藻生产供应二氧化碳，总共处理停留时间22h后(其中紫外光照射处理4min，活性污泥处理9h，微藻处理12.93h)，PTA 废水的CODcr含量为89mg/L，烟气中二氧化碳的捕集率达到93.5％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例4
含PTA的废水和烟气条件与实施例4相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为4.8，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期40h，处理后废水的CODcr含量为700mg/L。
实施例5
一个含有PTA废水的污水源每天排放量80吨，PTA废水的CODcr含量为17000mg/L，水温45℃，废水的pH值为4.5。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，活性污泥处理后的废水的pH值为6.02，CODcr含量为2080mg/L。之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为10v％的烟气为微藻生产供应二氧化碳，总共处理停留时间28h后(其中紫外光照射处理40min，活性污泥处理10h，微藻处理17.33h)，PTA废水的CODcr含量为129mg/L，烟气中二氧化碳的捕集率达到90.5％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例5
含PTA的废水和烟气条件与实施例5相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为4.5，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期36h，处理后废水的CODcr含量为1300mg/L。
实施例6
一个含有PTA废水的污水源每天排放量30吨，PTA废水的CODcr含量为23000mg/L，水温40℃，废水的pH值为4.2。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，活性污泥处理后的废水的pH值为5.95，CODcr含量为4810mg/L。之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为12.5v％的烟气为微藻生产供应二氧化碳，总共处理 停留时间30h后(其中紫外光照射处理12min，活性污泥处理10h，微藻处理19.8h)，PTA废水的CODcr含量为179mg/L，烟气中二氧化碳的捕集率达到91.3％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例6
含PTA的废水和烟气条件与实施例6相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为4.2，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期42h，处理后废水的CODcr含量为1500mg/L。
实施例7
一个含有PTA废水的污水源每天排放量15吨，PTA废水的CODcr含量为29000mg/L，水温40℃，废水的pH值为3.9。采用本发明提供的方法进行处理，首先采用波长为365nm的紫外光进行紫外光照射处理，将PTA分子进行分解，然后进行活性污泥预处理，活性污泥处理后的废水的pH值为5.89，CODcr含量为3284mg/L，之后水样进入微藻池进行微藻处理，同时通入二氧化碳含量为12v％的烟气为微藻生产供应二氧化碳，总共处理停留时间30h后(其中紫外光照射处理10min，活性污泥处理8h，微藻处理21.83h)，PTA废水的CODcr含量为209mg/L，烟气中二氧化碳的捕集率达到90.3％。反应器中的微藻定期置换，用于裂解制燃料气。
对比例7
含PTA的废水和烟气条件与实施例7相同，不同之处在于，采用传统的活性污泥法处理，其中将上述来自市政污水厂的活性污泥将与待处理的废水充分混合后，曝气。由于废水的pH值为3.9左右，污泥中的活性组分难以存活，传统方法无法处理含PTA废水，只能通过中和及稀释后进行处理，处理周期45h，处理后废水的CODcr含量为1700mg/L。
实施例8
与实施例1使用的废水以及处理步骤基本相同，区别仅在于在活性污泥预处理步骤使用的是未驯化的活性污泥，即上述来自市政污水厂的活性污泥。
处理后的PTA废水的CODcr含量为11000mg/L，烟气中二氧化碳的捕集率达到5％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例9
与实施例1使用的废水以及处理步骤基本相同，区别仅在于在活性污泥预处理步骤使用的是上述初步驯化后的活性污泥。
处理后的PTA废水的CODcr含量为450mg/L，烟气中二氧化碳的捕集率达到71％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例10
与实施例1使用的废水相同，处理步骤的不同之处在于未采用波长为365nm的紫外光对废水进行紫外光照射处理。即废水经活性污泥(8小时)和微藻(16小时)两步处理。处理后的PTA废水的CODcr含量为780mg/L，烟气中二氧化碳的捕集率达到85％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例11
与实施例1使用的废水相同，处理步骤的不同之处仅在于未采用微藻处理，即废水经紫外光照射和活性污泥处理，其中紫外光照射处理10min，活性污泥处理23小时50分钟。
处理后的PTA废水的CODcr含量为124mg/L，烟气中二氧化碳的捕集率为0％。
实施例12
与实施例1使用的废水相同，处理步骤的不同之处在于微藻处理步骤中，使用的微藻种类不同，在本实施例中微藻为微囊藻属(Microcystis)。
处理后的PTA废水的CODcr含量为205mg/L，烟气中二氧化碳的捕集率达到70％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例13
与实施例1的区别在于，紫外照射时间延长至80分钟，活性污泥处理时间为8小时，微藻处理时间为15.5小时。
处理后的PTA废水的CODcr含量为135mg/L，烟气中二氧化碳的捕集率达到91.2％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例14
与实施例1的区别在于，紫外照射时间为10分钟，活性污泥处理时间为4小时，微藻处理时间为19小时50分钟。
处理后的PTA废水的CODcr含量为92mg/L，烟气中二氧化碳的捕集率达到95.4％。反应器中的微藻定期置换，用于裂解制燃料气。
实施例15
与实施例1的区别在于，紫外照射时间为10分钟，活性污泥处理时间为11小时55分钟，微藻处理时间为11小时55分钟。
处理后的PTA废水的CODcr含量为112mg/L，烟气中二氧化碳的捕集率达到93.2％。反应器中的微藻定期置换，用于裂解制燃料气。

Claims (21)

  1. 一种酸性有机废水的处理及资源化利用方法，包括以下步骤：
    (1)将酸性有机废水进行活性污泥处理；
    (2)将步骤(1)处理后的酸性有机废水进行微藻处理。
  2. 根据权利要求1所述的方法，其特征在于，所述酸性有机废水为对苯二甲酸废水；和/或步骤(1)处理之前酸性有机废水的CODcr含量为3000-30000mg/L，和/或所述酸性有机废水的pH值为1-5。
  3. 根据权利要求1或2所述的方法，其特征在于，步骤(1)中使用的活性污泥为驯化后的活性污泥，优选所述活性污泥的驯化方法包括：
    第一阶段驯化：将处理市政污水用的活性污泥采用CODcr含量为3000-5000mg/L，pH值为1-5的酸性废水培养8-10天；
    优选地，第一阶段驯化的培养温度均为20-28℃，溶氧量控制在2-4mg/L。
  4. 根据权利要求1-3中任一项所述的方法，其特征在于，所述活性污泥的驯化方法还包括在第一阶段驯化之后的第二阶段驯化：用CODcr含量分别为6000-8000mg/L、9000-15000mg/L、16000-30000mg/L的酸性有机废水依次对第一阶段驯化后的活性污泥进行培养，培养时间均为1-3天；
    优选地，在第二阶段驯化过程中，添加N和P营养物质，氮源由尿素提供，磷源由磷酸氢二钾提供，比例为COD：N：P＝(95-102)：(0.8-1.3)：(0.7-1.2)；
    优选地，第二阶段的培养温度均为20-28℃，溶氧量控制在2-4mg/L。
  5. 根据权利要求1-4中任一项所述的方法，其特征在于，所述活性污泥中的微生物包括含量占总微生物的10％以上，优选150％以上，更优选20-25％以上的绿菌纲(Chlorobia)。
  6. 根据权利要求1-5中任一项所述的方法，其特征在于，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)、鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌纲(Chlorobia)，其总量占总微生物的50％以上，优选60％以上，更优选70％以上。
  7. 根据权利要求1-6中任一项所述的方法，其特征在于，所述活性污泥中的微生物包括15-25％的α-变形菌(Alphaproteobacteria)、10-15％的鞘脂杆菌纲(Sphingobacteriia)、15-25％的β-变形菌(Betaproteobacteria)和20-25％的绿菌纲，优选20-22％的α-变形菌，11-13％的鞘脂杆菌纲，18-21％的β-变形菌以及21-25％的绿菌纲。
  8. 根据权利要求1-7中任一项所述的方法，其特征在于，所述活性污泥中的微生物 包括α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)；
    优选地，α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)的总量占总微生物的50％以上，优选60％以上，更优选70％以上；
    优选地，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)30-40％，鞘脂杆菌纲(Sphingobacteriia)20-25％和异常球菌纲(Deinococci)8-12％；
    更优选地，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)33-36％，鞘脂杆菌纲(Sphingobacteriia)22-24％和异常球菌纲(Deinococci)9-10％。
  9. 根据权利要求1-8中任一项所述的方法，其特征在于，所述活性污泥处理的时间为5-96h，优选为5-48h；和/或所述微藻处理的时间为5-240h，优选为12-36h。
  10. 根据权利要求1-9中任一项所述的方法，其特征在于，所述微藻处理中使用的微藻为小球藻属；优选地，在使用前在光生物装置中将微藻驯化处理，驯化处理的条件优选为使用待处理酸性有机废水培养10-16天，同时给予光照，优选光照强度为3000-4100lux。
  11. 根据权利要求1-10中任一项所述的方法，其特征在于，所述方法还包括在活性污泥处理之前对酸性有机废水进行紫外光照射处理；优选地，所述紫外光照射处理的时间为4-500min，更优选为5-60min。
  12. 根据权利要求1-11中任一项所述的方法，其特征在于，所述方法还包括在所述微藻处理中，采用工业驰放气和/或生物质气源中的二氧化碳作为微藻生长的碳源；优选地，所述工业驰放气为烟气，所述烟气中二氧化碳的含量可以为8v％-15v％，优选为10v％-12.5v％。
  13. 根据权利要求1-12中任一项所述的方法，其特征在于，所述方法还包括将微藻处理使用后的微藻回收，作为生物质能源的材料用于裂解制生物质燃料气。
  14. 一种活性污泥的驯化方法，包括：
    第一阶段驯化：将处理市政污水用的活性污泥采用COD值为3000-5000mg/L，pH值为1-5的酸性有机废水培养8-10天；
    优选地，第一阶段驯化的培养温度均为20-28℃，溶氧量控制在1-5mg/L，优选2-4mg/L。
  15. 根据权利要求14所述的驯化方法，其特征在于，所述驯化方法还包括在第一阶段驯化之后的第二阶段驯化：用COD值分别为6000-8000mg/L、9000-15000mg/L、16000-30000mg/L的酸性有机废水依次对第一阶段驯化后的活性污泥进行培养，培养时间均为1-3天；优选地，第二阶段的培养温度均为20-28℃，溶氧量控制在2-4mg/L，1-5mg/L， 优选2-4mg/L。
  16. 根据权利要求15所述的驯化方法，其特征在于，在第二阶段驯化过程中，添加N和P营养物质，氮源由尿素提供，磷源由磷酸氢二钾提供，比例为COD：N：P＝(95-102)：(0.8-1.3)：(0.7-1.2)；
  17. 一种适用于处理酸性有机废水的活性污泥，所述活性污泥中的微生物包括含量占总微生物的10％以上，优选15％以上，更优选20-25％的绿菌纲(Chlorobia)。
  18. 根据权利要求17所述的活性污泥，其特征在于，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)、鞘脂杆菌纲(Sphingobacteriia)、β-变形菌(Betaproteobacteria)和绿菌纲(Chlorobia)，其总量占总微生物的50％以上，优选60％以上，更优选70％以上。
  19. 根据权利要求17或18所述的活性污泥，其特征在于，所述活性污泥的微生物中包括15-25％的α-变形菌(Alphaproteobacteria)、10-15％的鞘脂杆菌纲(Sphingobacteriia)、15-25％的β-变形菌(Betaproteobacteria)和20-25％的绿菌纲，优选地，所述活性污泥中的微生物中包括所述20-22％的α-变形菌，11-13％的鞘脂杆菌纲，18-21％的β-变形菌以及21-25％的绿菌纲。
  20. 根据权利要求17-19中任一项所述的活性污泥，其特征在于，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)；
    优选地，α-变形菌(Alphaproteobacteria)，鞘脂杆菌纲(Sphingobacteriia)和异常球菌纲(Deinococci)的总量占总微生物的50％以上，优选60％以上，更优选70％以上；
    优选地，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)30-40％，鞘脂杆菌纲(Sphingobacteriia)20-25％和异常球菌纲(Deinococci)8-12％；
    更优选地，所述活性污泥中的微生物包括α-变形菌(Alphaproteobacteria)33-36％，鞘脂杆菌纲(Sphingobacteriia)22-24％和异常球菌纲(Deinococci)9-10％。
  21. 根据权利要求14-16中任一项所述的驯化方法得到的活性污泥和/或权利要求17-20中任一项所述的活性污泥在酸性有机废水处理中的应用。
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