WO2016011785A1 - 养殖微藻与工业废气脱硝联合的方法及用于该方法的系统 - Google Patents

养殖微藻与工业废气脱硝联合的方法及用于该方法的系统 Download PDF

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WO2016011785A1
WO2016011785A1 PCT/CN2015/000181 CN2015000181W WO2016011785A1 WO 2016011785 A1 WO2016011785 A1 WO 2016011785A1 CN 2015000181 W CN2015000181 W CN 2015000181W WO 2016011785 A1 WO2016011785 A1 WO 2016011785A1
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microalgae
culture
nox
algae
waste gas
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PCT/CN2015/000181
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English (en)
French (fr)
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荣峻峰
周旭华
程琳
朱俊英
黄绪耕
宗保宁
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority to AU2015292150A priority Critical patent/AU2015292150B2/en
Priority to KR1020177005082A priority patent/KR102373138B1/ko
Priority to EP15824186.9A priority patent/EP3173472B1/en
Priority to ES15824186T priority patent/ES2891333T3/es
Priority to JP2017503810A priority patent/JP6698624B2/ja
Priority to US15/328,331 priority patent/US10533154B2/en
Publication of WO2016011785A1 publication Critical patent/WO2016011785A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/12—Unicellular algae; Culture media therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/50—Inorganic acids
    • B01D2251/504—Nitric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/802—Visible light
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/12—Unicellular algae; Culture media therefor
    • C12N1/125—Unicellular algae isolates
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/89—Algae ; Processes using algae
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a method for breeding microalgae and a method for combining microalgae culture with industrial waste gas denitration.
  • Microalgae are a wide variety of aquatic plants with a wide range of distribution. They are known as "sunlight-driven activation plants” through efficient photosynthesis and conversion of light energy into chemical energy of carbohydrates such as fat or starch. The use of microalgae to produce bioenergy and chemicals is expected to achieve both the dual purpose of replacing fossil energy and purifying waste gas and sewage.
  • microalgae and bacteria there are complex ecological relationships between microalgae and bacteria. Some specific microalgae and bacteria may promote each other, while others may inhibit each other.
  • a known difficulty in the cultivation of microalgae is the presence of a large number of harmful bacteria in water and air, which are detrimental to the growth of microalgae and, in severe cases, to failure in farming.
  • sterilized state can be achieved by using a closed culture system and strict sterilization, however, for large-scale cultivation of microalgae, The cost of this method is too expensive.
  • Nitrogen oxides (NOx) in industrial waste gas is one of the main atmospheric pollutants. It not only produces photochemical smog and acid rain, but also causes serious greenhouse effect. It is the main cause of atmospheric haze, so the problem of denitration of industrial waste gas It has received increasing attention from people.
  • the denitration method of industrial waste gas can be divided into dry method and wet method.
  • Catalytic reduction (SCR) and non-catalytic reduction (SNCR) are common dry denitration methods. These two methods have high investment and operating costs, and reduce NOx to low-value nitrogen, which does not achieve resource utilization.
  • SCR catalytic reduction
  • SNCR non-catalytic reduction
  • Wet denitration is a method of fixing NOx in exhaust gas to the absorption liquid.
  • the NOx in industrial waste gas is mainly NO (generally 90%). More than %), while NO is extremely insoluble in water, so measures need to be taken to solve the solubility problem of NO; second, nitrite or nitrite is inevitably formed during absorption, and nitrous acid or nitrite is a highly toxic substance. Therefore, measures need to be taken to solve the problem of separation, utilization or disposal.
  • nitrogen is one of the most consumed and most deficient nutrients in the growth of microalgae.
  • a large amount of nitrogen fertilizer is expensive for breeding microalgae. Therefore, if the cultured microalgae can be combined with industrial waste gas denitrification, on the one hand, NOx can be used to provide nitrogen fertilizer for microalgae growth, thereby reducing the cost of breeding microalgae; on the other hand, it can purify exhaust gas, reduce NOx emissions, and produce more Great environmental benefits.
  • the amount of NOx produced by the chemical industry is huge. If microalgae is used to fix NOx in industrial waste gas, it is necessary to match the rate of fixed NOx of microalgae with the rate of industrial NOx emission, and to minimize the area of microalgae culture equipment. . Generally, the efficiency of self-supporting of light energy is less than 30g.m -2 .d -1 , and the efficiency of large-scale outdoor culture is generally lower than 10g.m -2 .d -1 . The industrial waste gas denitration with such efficiency will occupy a large amount of Land, so it is necessary to further improve the breeding efficiency of microalgae.
  • Adding organic carbon source for heterotrophic culture or photo-energy is a feasible method to accelerate the growth of microalgae.
  • algae liquid is highly susceptible to harmful bacteria pollution, resulting in bacterial growth significantly faster than microalgae. Growth, which leads to failure of microalgae farming.
  • microalgae Large-scale cultivation of microalgae requires a large amount of water, and if it is not recycled, it will greatly increase the cost of breeding. It is known that most microalgae cannot adapt to high concentrations of ammonium salt solutions. For example, ammonium sulfate is often used as an inhibitor of microalgae in the prior art; while using nitrate salts to provide a nitrogen source for microalgae, it will be difficult to recycle water for culture. The reason is that metal ions will accumulate in the aquaculture water body, resulting in a gradual increase in salinity, and high salinity usually has a significant inhibitory effect on the growth of microalgae.
  • the first object of the present invention is to improve the breeding efficiency of microalgae, in particular to improve the breeding efficiency of heterotrophic culture and light energy.
  • a second object of the present invention is to avoid aseptic processing in heterotrophic culture and photo-energy.
  • the third object of the present invention is to organically combine microalgae culture with industrial waste gas denitration, which can utilize NOx to provide a nitrogen source for microalgae growth, and avoid mutual mutual occurrence due to different exhaust gas emissions and microalgae cultivation conditions. influences.
  • a fourth object of the invention is to use nitric acid / An aqueous solution of hydrogen peroxide is used as an absorbing liquid to denitrify industrial waste gas to avoid the formation of toxic nitrous acid; and to increase the hydrogen peroxide utilization rate of the process.
  • the invention includes, for example, the following aspects.
  • the present invention provides a method for efficiently breeding microalgae, characterized in that EM bacteria are added to the algae solution during the aquaculture process.
  • the present invention provides a method of breeding microalgae, wherein at least one of a nitrogen source, a phosphorus source, and a carbon source is provided in the form of an alkali metal nutrient in a culture medium for cultured microalgae;
  • the pH of the algae solution is adjusted with nitric acid and/or nitrous acid.
  • the present invention provides a combined method for the cultivation of microalgae and industrial waste gas denitrification, comprising the steps of:
  • step (2) drying the algae obtained in the step (2) to obtain a drying step of the microalgae product
  • the NOx-immobilized nutrient stream obtained from the step (3) provides a nitrogen source for the microalgae culture of the step (1).
  • step (3) can be carried out in various ways.
  • the combined process involves an acid process wherein the step (3) comprises:
  • step (ii) mixing the culture residue obtained in the step (2) with the nitric acid and/or nitrous acid (preferably nitric acid and optionally nitrous acid) obtained in the step (i) to effect denitration of the industrial waste gas.
  • nitric acid and/or nitrous acid preferably nitric acid and optionally nitrous acid
  • the mixed solution is used as the NOx-immobilized nutrient stream to provide a nitrogen source for the microalgae culture process of step (1).
  • the combined process involves an alkaline process wherein the step (3) comprises:
  • the NOx-immobilized nutrient stream obtained by this step (i') provides a nitrogen source for the cultured microalgae process of step (1).
  • the present invention provides a system for a combined method for the cultivation of microalgae and industrial off-gas denitration comprising, optionally from upstream to downstream:
  • a NOx fixing unit for performing a denitration reaction and providing a nutrient stream in which NOx is fixed
  • microalgae culture device for performing microalgae cultivation using the NOx-immobilized nutrient stream
  • a separator for separating the algae liquid harvested from the microalgae culture device into algae mud and culture residue
  • a dryer for drying the algal mud to obtain a microalgae product.
  • the NOx fixation unit has a NOx-containing industrial waste gas inlet, a cultured residue inlet, a NOx-immobilized nutrient stream outlet, and a purified industrial waste gas outlet, and optionally a nutrient solution inlet.
  • the microalgae culturer has a NOx-enhanced nutrient stream inlet, a algae seed inlet and an algae liquid outlet, and optionally a nutrient solution inlet and optionally an EM bacteria inlet.
  • the separator has an algae solution inlet, an algal mud outlet, and a culture residue outlet.
  • the circulation line connects the culture residue outlet of the separator and the culture residue inlet of the NOx fixation unit.
  • the NOx fixation unit or microalgae culturer has a nutrient solution inlet.
  • the microalgae culturer has a nutrient solution inlet in an alkaline process.
  • the combined process involves an acid process wherein the NOx fixation unit comprises a denitration reactor and a NOx fixed nutrient stream dispenser.
  • the combined process involves an alkaline process wherein the NOx fixation unit is a denitration reactor.
  • At least one of a nitrogen source, a phosphorus source and a carbon source is provided in the form of an alkali metal nutrient in the medium in which the microalgae are cultured.
  • the pH of the algal solution is adjusted with nitric acid and/or nitrous acid during the cultivation process.
  • the nitrogen source is provided in the form of an alkali metal nitrate and/or an alkali metal nitrite in the medium in which the microalgae are cultured.
  • the microalgae is cultured in a heterotrophic or photosynthetic manner.
  • the organic carbon source used is selected from the group consisting of sugars, organic acids, organic acid salts, alcohols, and cellulose hydrolysates. And at least one of the starch hydrolysates; preferably at least one of glucose, fructose, acetic acid, sodium acetate, lactic acid, ethanol, methanol, and cellulose hydrolyzate, more preferably glucose.
  • the concentration of the organic carbon source used is controlled at 1 g/L algae solution to 30 g/L algae solution, preferably Control in 2g / L algae liquid ⁇ 10g / L algae liquid.
  • the culture method is light self-supporting or light energy, and the light intensity is 1000-200,000 lux.
  • the method for cultivating microalgae according to the present invention further comprises the steps of separating the algal mud from the harvested algae liquid and recycling the culture residue obtained after separating the algal mud for the cultivation of the microalgae.
  • the prior art believes that the use of nitrate in microalgae culture is sufficient as a nitrogen source, but in some cases the accumulation of metal ions contained in the nitrate may inhibit algae growth.
  • the acid process when the acid process is employed, no additional nitrate is added, and no new metal cations are introduced into the process, so that the metal cations do not accumulate in the process.
  • EM bacteria are added to the algal fluid during the culture of the microalgae.
  • the amount of the M bacteria added is 1 ⁇ 10 5 / L algae liquid ⁇ 9 ⁇ 10 8 / L algae liquid, preferably 1 ⁇ 10 6 / L algae liquid ⁇ 5 ⁇ 10 8 / L algae liquid, further preferably It is 1 ⁇ 10 6 / L algal liquid ⁇ 1 ⁇ 10 8 / L algae liquid. .
  • step (i) of the combined process the NOx in the industrial off-gas is converted to nitric acid by wet denitrification.
  • the wet method The absorption liquid for absorbing NOx in the nitrate is composed of 0.5 m% to 58 m% of nitric acid, 0.001 m% to 25 m% of hydrogen peroxide, and the balance of water.
  • the absorbing liquid in the wet denitration, is composed of 10% to 25% by weight of nitric acid, 0.1% to 1% by mole of hydrogen peroxide, and the balance of water.
  • the present invention achieves the following technical effects.
  • the pH of the algae solution is adjusted with nitric acid and/or nitrous acid during the cultivation of the microalgae, which greatly improves the efficiency of the cultured microalgae.
  • microalgae culture and industrial waste gas denitrification are two relatively independent processes, avoiding the mutual influence caused by different exhaust gas emissions and microalgae aquaculture conditions, and avoiding the problem that a large amount of NO is insoluble in water and difficult to fix.
  • the use of NOx in industrial waste gas to provide a source of nitrogen to the microalgae without the need for additional lye can make the method of the present invention less costly to grow.
  • the invention avoids the problem of accumulation of metal ions and enables the aquaculture water body to be recycled.
  • the addition of EM bacteria to the algae liquid can effectively inhibit the growth of harmful bacteria and greatly increase the growth rate of the microalgae.
  • This feature makes the invention not need to be sterilized and sterilized when heterotrophic culture or light energy is maintained, thus giving the present invention a greater advantage.
  • an aqueous solution of a low concentration of hydrogen peroxide and a low concentration of nitric acid is used as an absorption liquid for denitration of industrial waste gas, and the decomposition rate of hydrogen peroxide is lower and the effective utilization rate is high.
  • dilute nitric acid is produced while denitrating industrial exhaust gas, and the dilute nitric acid does not contain toxic nitrous acid, which is more advantageous for use as a nitrogen source for breeding microalgae.
  • Figure 1 shows the microalgae growth curve of light energy autotrophic.
  • Figure 2 shows the growth curve of microalgae with light energy.
  • Figure 3 is a graph showing the growth curve of microalgae using nitrate as a nitrogen source.
  • Figure 4 and Figure 5 show the growth curve of microalgae with a large amount of organic carbon source added.
  • Figure 6 is a schematic illustration of a NOx fixation process.
  • Fig. 7 and Fig. 8 are graphs showing the growth curve of microalgae using a nutrient stream in which NOx is fixed as a nitrogen source.
  • Figure 9 is a graph showing the growth curve of microalgae added with EM bacteria under conditions of no photo-heterotrophic conditions.
  • Figure 10 is a graph showing the NOx fixing rate as a function of time.
  • Figure 11 shows the growth curve of chlorella under different conditions.
  • Figure 12 shows the growth curve of spirulina under different conditions.
  • Figure 13 is a schematic illustration of the overall process flow of the combined process in accordance with the present invention.
  • Figure 14 is a schematic illustration of the acid process flow in accordance with the combined process of the present invention.
  • Figure 15 is a schematic flow diagram of an acid process in accordance with the combined method of the present invention in combination with additional light energy autotrophy.
  • A a gas containing NOx
  • B a nutrient stream in which NOx is fixed
  • G wet microalgae
  • the medium refers to a body of water in which microalgae grows during microalgae cultivation, and all necessary nutrients for the growth of microalgae have been included unless otherwise specified.
  • a nutrient stream refers to a stream containing one or more nutrient sources such as a nitrogen source, a phosphorus source or a carbon source for formulation into a nutrient base unless otherwise specified.
  • the algal fluid is a system formed by adding microalgae to the medium unless otherwise specified.
  • any matters or matters not mentioned are directly applicable to those known in the art without any change.
  • any of the embodiments described herein can be freely combined with one or more other embodiments described herein, and the resulting technical solution or technical idea is considered to be part of the original disclosure or original description of the present invention, and should not be It is considered to be new content that has not been disclosed or anticipated herein, unless it is apparent to those skilled in the art that the combination is clearly unreasonable.
  • the present invention provides a method for cultivating microalgae, wherein at least one of a nitrogen source, a phosphorus source and a carbon source is provided in the form of an alkali metal nutrient in a culture medium for cultivating microalgae, wherein during the breeding process The pH of the algae is adjusted with nitric acid and/or nitrous acid.
  • the culture method may be self-supporting of light energy (in the case of illumination, only using an inorganic carbon source such as CO 2 growth), heterotrophic culture (heterotrophic culture refers to growth using only an organic carbon source) or light energy (Photo-energy is the simultaneous use of inorganic carbon sources such as CO 2 and organic carbon sources under illumination.
  • microalgae requires the necessary conditions. For example, algae requires appropriate temperature, sufficient light (self-supporting light energy or light energy), sufficient water, CO 2 and nitrogen and phosphate fertilizers in the form of nutrient solution. A substance that regulates dissolved oxygen in the algae solution, has a pH in an appropriate range, and the like. Although these conditions are different for different microalgae, these are known in the art.
  • the culture temperature is 15 to 40 ° C, preferably 25 to 35 ° C; the pH of the algal solution is 6 to 11, and the preferred pH of the algal solution is 7 to 9.
  • the light intensity is 1000 to 200,000 lux, and the preferred light intensity is 5,000 to 150,000 lux.
  • the inventors have found through extensive experiments that the cultivation method of light energy self-supporting or light energy, especially when microalgae metabolize alkali metal nitrate, alkali metal nitrite, alkali metal carbonate, alkali metal hydrogencarbonate
  • the alkali metal phosphates, the alkali metal hydrogen phosphates, or any combination thereof if the CO 2 is not introduced into the algae solution during the culture of the microalgae or the pH adjuster is not added, the pH of the algae liquid will be Ascending, especially when the microalgae metabolize alkali metal nitrate, alkali metal nitrite or a combination thereof, the pH value of the algae liquid rises rapidly.
  • the cultured microalgae has a pH of 6 to 11.
  • the present invention preferably adjusts the algae liquid with nitric acid and/or nitrous acid. pH value.
  • the present invention is not limited to the type of microalgae. According to the present invention, it is preferred to breed microalgae suitable for oil production so that both bioenergy and exhaust gas pollutants can be reduced.
  • heterotrophic culture or light energy supplementation will increase the cost of some cultures due to the use of organic carbon sources, the breeding efficiency is greatly improved, which simplifies the subsequent processing. Therefore, if sterile farming can be avoided, it can avoid a large amount of consumption. Steam rigorously sterilizes the system, significantly reducing the cost of farming.
  • those which are heterotrophic or photo-energy such as chlorella, Scenedesmus, Spirulina or Spirulina are particularly preferred.
  • these microalgae are cultured by heterotrophic culture or photo-energy, as long as a certain amount of EM bacteria is added, even if sterilization is not carried out, the culture will proceed smoothly and the growth rate of microalgae will be greatly accelerated. Even if the water source contains a large amount of harmful bacteria and/or open culture, the result is the same; when EM bacteria are not added, heterotrophic culture or light energy maintenance usually fails.
  • the heterotrophic culture or the photo-energy it is preferred not to perform a sterilization operation, nor to add a bactericide, but to add EM bacteria.
  • the EM bacteria (Effective Microorganisms) are known in the art, and are mainly composed of dozens of filamentous flora belonging to photosynthetic bacteria, lactic acid bacteria, yeast groups, Gram-positive actinomycetes, and fermentation lines.
  • the microbial composition is a commercially available live bacterial preparation. Said EM
  • the bacteria can be prepared according to the prior art, or can be obtained by commercial use, and the fermentation should be carried out according to the existing knowledge or the description of the commercially available preparation before use.
  • the amount of EM bacteria should be sufficient to accelerate the growth of microalgae, and it should not be used because it is too small to be used, and it cannot compete with microalgae for excessive consumption of nutrients due to excessive use.
  • Any EM bacteria addition method (such as one-time addition or multiple additions) and any EM bacteria dosage can be used as long as it can meet the needs of accelerating the growth of microalgae.
  • the EM bacteria are added in an amount of 1 ⁇ 10 5 / L algae liquid to 9 ⁇ 10 8 / L algae liquid, preferably 1 ⁇ 10 6 / L algae liquid ⁇ 5 ⁇ 10 8 / L algae
  • the liquid is more preferably 1 ⁇ 10 6 /L algal liquid to 1 ⁇ 10 8 /L algae liquid.
  • available organic carbon sources include, but are not limited to, at least one of sugars, organic acids, organic acid salts, alcohols, cellulose hydrolysates, and starch hydrolyzates; It may be selected from at least one of glucose, fructose, acetic acid, sodium acetate, lactic acid, ethanol, methanol, and cellulose hydrolysate, and the preferred option is glucose.
  • any means of supplementing nutrients may be used, such as stepwise addition or continuous addition, as long as the amount of nutrients can be controlled within an appropriate range.
  • the concentration of the organic carbon source is generally controlled to 1 g/L algal liquid to 30 g/L algae liquid, preferably controlled to 2 g/L algal liquid to 10 g/L algae liquid.
  • the organic carbon source can be added in one portion or in multiple portions.
  • the metal ion is sodium and/or potassium.
  • the nitrogen source is preferably an alkali metal nitrate and/or an alkali metal nitrite.
  • the phosphorus source is preferably an alkali metal phosphate and/or an alkali metal hydrogen phosphate.
  • a part of the carbon source may be an alkali metal carbonate and/or an alkali metal hydrogencarbonate.
  • all or a majority of the carbon source is provided in the form of CO 2 when self-supporting with light energy.
  • the nitrogen source, the phosphorus source, and the carbon source are used in an amount according to a conventionally known technique.
  • the nitrogen source is used in an amount of 0.1 to 400 mmol/L, preferably 10 to 300 mmol/L. Further, it is preferably 20 to 200 mmol/L.
  • the method further comprises the steps of separating the microalgae from the harvested algae liquid and recycling the culture residue obtained after the isolation of the microalgae for the cultivation of the microalgae.
  • the invention provides a combined method for the cultivation of microalgae and industrial waste gas denitration, comprising the following steps:
  • step (2) drying the algae obtained in the step (2) to obtain a drying step of the microalgae product
  • the NOx-immobilized nutrient stream obtained from the step (3) provides a nitrogen source for the microalgae culture of the step (1).
  • step (3) can be carried out in various ways.
  • the combined process of the present invention involves an acid process wherein said step (3) comprises:
  • step (ii) mixing the culture residue obtained in the step (2) with the nitric acid and/or nitrous acid (preferably nitric acid and optionally nitrous acid) obtained in the step (i) to effect denitration of the industrial waste gas.
  • nitric acid and/or nitrous acid preferably nitric acid and optionally nitrous acid
  • the mixed solution is used as the NOx-immobilized nutrient stream to provide a nitrogen source for the microalgae culture process of step (1).
  • the combined process involves an alkaline process wherein the step (3) comprises:
  • the culture residue obtained in the step (2) directly fixes NOx in the industrial waste gas.
  • the nitrogen-derived process is used to provide a source of nitrogen for the cultured microalgae process of step (1).
  • the step (1) may be carried out by any of the specific embodiments described in the aforementioned "Method for Breeding Microalgae", and may have the features, steps, conditions or combinations thereof described therein.
  • the NOx content in the industrial waste gas to be treated is not particularly limited.
  • the NOx content in industrial waste gas ranges from a few hundred ppm by volume to several thousand ppm, such as between 100 ppm and 5000 ppm.
  • the mole fraction of NO is ⁇ 80% based on the total amount of NOx; further, in the industrial waste gas, NO is occupied by the total amount of NOx.
  • the mole fraction is ⁇ 90%.
  • step (i) in the acid process, can be used to convert NOx in industrial waste gas to nitric acid and/or nitrous acid by any existing method.
  • microalgae are not able to metabolize NO 2 - .
  • a suitable method is available, such as an oxidative absorption method using nitric acid/hydrogen peroxide as an absorbent.
  • microalgae capable of simultaneously metabolizing NO 3 - and NO 2 - , such as chlorella, single needle algae, Scenedesmus or spirulina screened by the present invention, in which case there is substantially no conversion of NO 2 - The problem.
  • NO 3 - and NO 2 - such as chlorella, single needle algae, Scenedesmus or spirulina screened by the present invention.
  • the acid process for heterotrophic culture it is preferred to use the acid process for spirulina culture.
  • the NOx in the industrial waste gas is preferably converted to nitric acid by wet denitration.
  • the absorption liquid for absorbing NOx in wet denitration is composed of 0.5 m% to 58 m% of nitric acid, 0.001 m% to 25 m% of hydrogen peroxide, and the balance of water.
  • Such an embodiment is thus referred to as an acid process.
  • the present inventors have found that, for the acid process, although a high concentration of nitric acid/low concentration hydrogen peroxide aqueous solution or a high concentration hydrogen peroxide/low concentration nitric acid aqueous solution can effectively absorb low oxidation degree NOx, both of them All methods have defects in that hydrogen peroxide decomposes faster and has a large loss.
  • an aqueous solution of low concentration hydrogen peroxide/low concentration nitric acid the decomposition of hydrogen peroxide is slow, whereas the aqueous solution of low concentration hydrogen peroxide/low concentration nitric acid has a low absorption activity for low oxidation degree NOx.
  • the low concentration hydrogen peroxide/low concentration nitric acid aqueous solution has a low absorption activity for low oxidation degree NOx
  • the aqueous solution has a low oxidation degree NOx with time.
  • the absorption activity is slowly increased, and after a period of time (activation phase), the absorption activity of the aqueous solution to low oxidation degree NOx enters a high level of stable period.
  • the low concentration hydrogen peroxide/low concentration nitric acid absorption fluid of the present invention has undergone the activation phase prior to use in absorbing NOx.
  • the absorbing liquid is preferably composed of 10% to 25% by weight of nitric acid, 0.1% to 1% by mole of hydrogen peroxide and the balance of water; more preferably from 10% to 25% by weight.
  • Nitric acid, 0.2m% to 1m% of hydrogen peroxide and the balance of water are preferred.
  • the activation phase includes: 10m% to 25m% nitric acid, 0.1m% to 1m%
  • the solution of hydrogen peroxide and the balance water is contacted with the NOx-containing gas, and the activation step is completed when the denitration activity of the solution no longer continues to rise.
  • the mole fraction of NO is ⁇ 80% based on the total amount of NOx.
  • the NOx-containing gas for activating the absorbing liquid may be the industrial exhaust gas.
  • the denitration temperature may be -10 ° C to 40 ° C
  • the denitration pressure may be 0.1 Mpa to 1 Mpa; the preferred denitration temperature and pressure are normal temperature and normal pressure.
  • the manner of contacting the industrial exhaust gas with the active absorbing liquid in the aforementioned wet denitration is not particularly limited, and for example, one of the following (A), (B), (C) or any combination thereof may be employed:
  • an absorption tower or a plurality of absorption towers connected in series may be employed; preferably, one absorption tower or two to three absorption towers connected in series are used.
  • the type of the absorption tower is not particularly limited, and for example, one of the following or a combination thereof may be used: a plate type absorption tower, a bubble absorption tower, a stirring bubble absorption tower, and the absorption liquid is dispersed in a droplet form in the gas phase.
  • the spray tower, the packed absorption tower and the falling film absorption tower are preferably used; a bubbling absorption tower or a stirring bubbling absorption tower is preferably used.
  • step (1) it is preferred to adjust the pH of the culture medium by means of microalgae metabolism in step (1) such that the pH of the culture residue obtained from step (2) is >8, more preferably the pH of the culture residue. It is 9-11.
  • the cultivation method of photoautotrophic or photoenergetic especially when the microalgae medium contains alkali metal nitrate, alkali metal nitrite, alkali metal carbonate, alkali metal hydrogencarbonate
  • the pH of the algae liquid rises if the CO 2 (or pH adjuster) is not provided or provided during the culture of the microalgae. the trend of.
  • CO 2 (or pH adjuster) can be provided or not provided in the later stage of breeding microalgae, and the algae liquid at the end of the culture is made alkaline by the metabolism of microalgae, so that the microalgae can be separated.
  • the cultured residual liquid fixes NOx in the exhaust gas or neutralizes the acid solution after fixing the NOx, and then uses it to provide the necessary nitrogen source for the cultured microalgae.
  • the microalgae culture step by adjusting the supply of CO 2 to such that the pH of the culture raffinate> 8, more preferably 9 to 11.
  • the inventors have found that the alkaline culture residue after separation of the microalgae can efficiently fix NOx in the exhaust gas or neutralize the acid solution after fixing the NOx to obtain a solution containing NO 3 - and/or NO 2 - .
  • the solution can directly supply nitrogen source for the next batch of microalgae cultivation. After the nitrogen source is metabolized by the microalgae, the algae liquid will be made alkaline again. Through such a mode, the microalgae culture medium and industrial waste gas denitration process can be carried out.
  • microalgae cultivation and “exhaust gas denitrification” become two relatively independent processes, avoiding the mutual influence of the two.
  • the lye absorption/fixation method is a mature exhaust gas denitration process, and there are many studies on the absorption/fixation of exhaust NOx by an alkaline aqueous solution, and any of these existing methods can be employed in the present invention. It is known that in order to completely fix NO, an oxidation tower may be added in front of the alkali absorption tower to oxidize NO to NO 2 by using residual oxygen in the exhaust gas or adding ozone, thereby providing an optimum oxidation degree for the alkali fixation method (NO). 2 / NO molar ratio). Oxidation catalysts suitable for different situations are known in the art, such as activated carbon, activated carbon fiber, high silica zeolite Na-ZSM-5 zeolite or Siliceous ⁇ catalyst at room temperature to oxidize NO to NO 2.
  • the step (i') absorbs the fixed NOx by the alkali absorption method, and the absorption liquid for absorbing the fixed exhaust NOx adopts the culture residue obtained in the microalgae culture process, and does not provide these existing alkali fixation processes.
  • the nitrate salt step is extracted, and the solution obtained after fixing the NOx is directly supplied with a nitrogen source for the cultured microalgae.
  • microalgae capable of simultaneously metabolizing NO 3 - and NO 2 - , such as chlorella, single needle algae, Scenedesmus or spirulina screened by the present invention.
  • microalgae capable of withstanding a high alkali environment are preferred, and the cultivation of these microalgae can further increase the pH of the culture residue, thereby improving the efficiency of reacting with nitric acid and/or nitrous acid or fixing NOx.
  • the inventors have screened the following microalgae capable of resisting high alkali conditions, such as chlorella, unicellular algae, Scenedesmus or spirulina, which can grow healthily in a pH of 9-11.
  • those which are capable of rapidly increasing the pH of the algae liquid by self-metabolism when the CO 2 is not introduced are preferred, and the cultivation of these microalgae can further improve the efficiency of the process of breeding the microalgae.
  • the inventors screened out the following microalgae that can rapidly increase the pH value of algae, such as chlorella, single-needle algae, Scenedesmus or spirulina.
  • the microalgae can pH the algae in 1 to 24 hours. The value is increased to 9 to 11, so that the algae liquid satisfies the requirement of efficiently reacting with nitric acid and/or nitrous acid or absorbing fixed NOx.
  • the amount of the nitrogen-containing compound in the nutrient stream after the NOx is fixed from the step (i') to provide a nitrogen source for the microalgae is 0.1 to 400 mmol/L. It is preferably 10 to 300 mmol/L, and still more preferably 20 to 200 mmol/L.
  • Industrial waste gas may contain other pollutants such as SOx in addition to NOx, and those skilled in the art can confirm whether or not the exhaust gas contains a simple test (for example, by measuring the NOx fixation rate or measuring the degree of change of the microalgae growth rate). Or excessively containing contaminants that have a significant effect on the combined process of the invention.
  • the inventors have found that when the SOx content in the industrially emitted flue gas is high, the fixing efficiency of the refractory residue to NOx is lowered.
  • Those skilled in the art can also reduce the SOx in the exhaust gas to a level that does not significantly affect the implementation of the combined method of the present invention by conventionally known techniques, as desired.
  • industrially emitted flue gas especially coal-fired flue gas, contains a large amount of SOx, and therefore, for these industrial waste gases, it is necessary to remove the SOx contained in the exhaust gas of the present invention before denitration.
  • the industrial waste gas is preferably an industrial waste gas which does not contain SOx or undergoes a desulfurization treatment (removal of SOx in the exhaust gas).
  • microalgae culture and “industrial waste gas denitrification” in the present invention are two relatively independent processes, and the main function of the CO 2 -containing gas is to provide a carbon source for microalgae growth, which substantially does not contain SOx. And NOx.
  • the CO 2 -containing gas may be an industrial waste gas that has been subjected to purification treatment (removal of SOx and NOx in the exhaust gas), or an industrial waste gas that does not contain SOx and NOx.
  • the invention constructs a circular economy mode for reducing industrial waste gas pollutants and producing microalgae biomass. Using exhaust industrial emissions of NO x in nutrition as a nitrogen stream, while the emissions of pollutants, to obtain valuable microalgal biomass. In such a circular economy model, part of the cost of treating industrial waste gas is used to culture microalgae. The factory reduces waste gas, wastewater discharge and environmental pollution, forming a closed cycle, and only microalgae biomass is exported.
  • the combined method of the present invention can also be combined with additional microalgae culture, such as providing microalgae to the combined process at an initial stage, and in particular providing additional microalgae when the microalgae in the combined process described above require supplementation.
  • the additional microalgae culture can be a separate process from the microalgae cultivation step of the combined method to input microalgae to, for example, the microalgae culture, as needed, for example, see Figure 15.
  • This additional microalgal culture can also be incorporated into the combined process, for example downstream of the microalgae culture step described above.
  • the additional microalgae culture can be self-supporting, photo-energy and/or heterotrophic cultivation, so that the amount of microalgae produced is consistent with the need to supplement the above-described combined method.
  • the additional microalgae culture is self-supporting for light energy using methods known in the art, such as the process flow shown in Figure 15.
  • the present invention provides a system for a combined method for the cultivation of microalgae and industrial waste gas denitration comprising, optionally from upstream to downstream:
  • a NOx fixed unit having a NOx-containing industrial exhaust gas inlet, a cultured residual liquid inlet, a NOx-immobilized nutrient stream outlet, and a purified industrial waste gas outlet, and optionally a nutrient solution inlet for performing a denitration reaction and providing fixed NOx Nutritional logistics;
  • a microalgae culturer having a NOx-immobilized nutrient stream inlet, a algae seed inlet and an algae liquid outlet, and optionally a nutrient solution inlet, optionally an EM bacteria inlet, for micro-reserving the NOx-enriched nutrient stream Algae farming
  • a separator having an algae liquid inlet, an algae sludge outlet, and a culture residue outlet for separating the algae liquid harvested from the microalgae culture device into algae mud and culture residue;
  • a dryer for drying the algal mud to obtain a microalgae product.
  • the NOx fixing unit has a nutrient solution inlet.
  • the microalgae culturer has a nutrient solution inlet in an alkaline process.
  • the combined process involves an acid process wherein the NOx fixation unit comprises a denitration reactor and a NOx fixed nutrient stream dispenser.
  • the combined process involves an alkaline process wherein the NOx fixation unit is a denitration reactor.
  • one embodiment of the system of the present invention includes: a NOx fixation unit 1; a microalgae culture 2; a separator 3; and a dryer 4.
  • the NOx fixing unit 1 comprises: a denitration reactor 1-1; and a NOx fixed nutrient stream distributor 1-2 (see FIG. 14); and for the alkaline process, 1 is 1-1: Denitration reactor.
  • the NOx-containing gas A, the culture residue C from the separator 3 and optionally the nutrient solution E are sent to the NOx fixing unit 1, and the NOx-fixed nutrient stream B is obtained after the treatment.
  • Purified gas C subsequently, the NOx-immobilized nutrient stream B, the algae species D, and optionally the nutrient solution E from the NOx fixing unit 1 are sent to the microalgae culture unit 2; the cultured algae liquid is sent to the separator 3 points The wet microalgae (algae) G and the culture residue F are obtained; the algal mud G is sent to the dryer 4, and dried to obtain the microalgae product H.
  • the nutrient solution E is added to the NOx fixing unit 1 in an acid process.
  • the nutrient solution E is added to the microalgae culture unit 2 in an alkaline process.
  • Figure 14 illustrates an acid process consistent with the embodiment shown in Figure 13.
  • the NOx fixing unit 1 is constituted by the denitration reactor 1-1; and the NOx fixed nutrient stream dispenser 1-2. Accordingly, for the NOx fixing unit 1, a NOx-containing gas A and an appropriate aqueous solution (not shown) of a low concentration hydrogen peroxide/low concentration nitric acid as a NOx fixing liquid are sent to the denitration reactor 1-1.
  • the NOx-fixed nutrient stream and the purified gas C are obtained; and the NOx-fixed nutrient stream, the culture residue C from the separator 3 and the nutrient solution E are sent to the NOx fixing unit 1, and after the treatment A nutrient stream B in which NOx is fixed is obtained.
  • the remaining facilities and process flow are the same as the general embodiment shown in FIG.
  • Figure 15 illustrates a combination of the combined method of the present invention and an additional microalgae culture phase.
  • the combined process of the present invention has a process flow as shown in Figure 13, except that the algal species D supplied to the microalgae culture 2 is specifically derived from an additional microalgae cultivation process, which is light energy. Self-supporting process.
  • the additional microalgae cultivation process provides microalgae to the combined process at an initial stage, and in particular provides additional microalgae when the microalgae in the combined process described above requires replenishment.
  • the additional microalgae culture can be a separate process from the microalgae culture step of the combined process to input microalgae to, for example, the microalgae culturer as needed.
  • the present invention provides the following exemplified embodiments:
  • a method for cultivating microalgae characterized in that EM bacteria are added to the algae liquid during the aquaculture process.
  • microalgae is a microalgae capable of heterotrophic culture or light energy.
  • microalgae is selected from the group consisting of green algae or cyanobacteria.
  • microalgae is chlorella, Scenedesmus, Spirulina or Spirulina.
  • the organic carbon source used in microalgae culture is selected from the group consisting of sugars, organic acids, organic acid salts, alcohols, cellulose hydrolysates, and at least One; preferably at least one of glucose, fructose, acetic acid, sodium acetate, lactic acid, ethanol, methanol, cellulose hydrolysate, and cellulose hydrolyzate, more preferably glucose.
  • the method according to any one of the embodiments 1-8 characterized in that, when the culture method is self-supporting of light energy or light energy, the light intensity is 1000-200,000 lux.
  • the method according to any one of the embodiments 1-9 characterized in that, in the aquaculture process, the nitrate salt obtained by denitration of industrial waste gas is preferably used as a nitrogen source with NO3- and/or NO2-. And / or nitrosyl salt as a nitrogen source.
  • any one of a nitrogen source, a phosphorus source, and a carbon source is provided in the form of an alkali metal nutrient in the nutrient stream of the cultured microalgae; It is characterized in that the pH of the algal solution is adjusted with nitric acid and/or nitrous acid during the cultivation process.
  • the nitric acid is obtained by converting NOx in industrial waste gas into nitric acid by wet denitration;
  • the absorption liquid in wet denitration is 0.5 M% to 58 m% of nitric acid, preferably 10 m% to 25 m% of nitric acid, 0.001 m% to 25 m% of hydrogen peroxide, preferably 0.1 m% to 1 m% of hydrogen peroxide and the balance water.
  • a combined method for the cultivation of microalgae and industrial waste gas denitration comprising the following steps:
  • step (2) drying the algae obtained in the step (2) to obtain a drying step of the microalgae product
  • the NOx-absorbing nutrient stream obtained from the step (3) provides a nitrogen source for the microalgae culture of the step (1).
  • step (3) comprises:
  • step (3) comprises:
  • the gas containing CO 2 is used as the inorganic carbon source, preferably
  • the CO 2 -containing gas is a purified industrial waste gas or an industrial waste gas containing no SOx and NOx.
  • the amount of the nitrogen-containing compound is from 0.1 to 400 mmol/L, preferably in terms of nitrogen atom. It is 10-300 mmol/L, and still more preferably 20-200 mmol/L.
  • the industrial waste gas is an industrial waste gas containing no SOx or an industrial waste gas subjected to desulfurization treatment.
  • CO 2 or pH adjuster is not provided or provided, and the algae liquid at the end of the culture is cultured by the microalgae to metabolize the alkali metal nutrient;
  • the alkali metal nutrient salt is alkali metal nitrate and alkali.
  • a metal nitrite, an alkali metal carbonate, an alkali metal hydrogencarbonate, an alkali metal phosphate, an alkali metal hydrogen phosphate or a combination thereof is preferably an alkali metal nitrate and/or an alkali metal nitrite.
  • the invention provides the following exemplified embodiments:
  • a method for cultivating microalgae wherein at least one of a nitrogen source, a phosphorus source and a carbon source is provided in the form of an alkali metal nutrient in a nutrient stream for cultivating microalgae;
  • the pH of the algal solution is adjusted with nitric acid and/or nitrous acid.
  • microalgae is a microalgae capable of heterotrophic culture or light energy.
  • microalgae is a green alga or a cyanobacteria, preferably chlorella, Scenedesmus, Spirulina or Spirulina.
  • nitric acid is obtained by converting NOx in industrial waste gas into nitric acid by wet denitration; and the absorption liquid in wet denitration is 0.5 M% to 58 m% of nitric acid, preferably 10 m% to 25 m% of nitric acid, 0.001 m% to 25 m% of hydrogen peroxide, preferably 0.1 m% to 1 m% of hydrogen peroxide and the balance of water.
  • organic carbon source used is selected from the group consisting of sugars, organic acids, organic acid salts, alcohols, cellulose hydrolysates and at least one with starch hydrolysates.
  • a combined method for the cultivation of microalgae and industrial waste gas denitration comprising the following steps:
  • step (3) completing the NOx absorption fixing step for denitration of industrial waste gas by using the culture residue obtained in the step (2), which comprises:
  • the NOx-immobilized nutrient stream obtained from the step (3) provides a nitrogen source for the microalgae culture of the step (1).
  • the NOx in the industrial waste gas is converted into nitric acid by wet denitration; and the absorption liquid in the wet denitration is from 0.5 m% to 58 m%. It is preferably composed of 10% to 25% by weight of nitric acid, 0.001% to 25% by mole, preferably 0.1% to 1% by mole of hydrogen peroxide and the balance of water.
  • the nitrogen source is in the form of an alkali metal nitrate and/or an alkali metal nitrite.
  • a system for a combined method for the cultivation of microalgae and industrial off-gas denitration comprising, optionally from upstream to downstream:
  • a NOx fixing unit for denitration reaction of industrial waste gas and providing a nutrient stream that absorbs and fixes NOx;
  • microalgae culture device for performing microalgae cultivation using the NOx-immobilized nutrient stream
  • a separator for separating the algae liquid harvested from the microalgae culture device into algae mud and culture residue
  • a dryer for drying the algal mud to obtain a microalgae product.
  • the NOx absorbing unit has an industrial exhaust gas inlet containing NOx, a feed residue inlet, a nutrient stream outlet to which NOx is fixed, and a purified industrial waste gas outlet;
  • the microalgae culture device has a nutrient stream inlet to which NOx is fixed, an algae seed inlet, and an algae liquid outlet;
  • the separator has an algae liquid inlet, an algae sludge outlet, and a culture residue outlet;
  • the circulation line connects the culture residue outlet of the separator and the culture residue inlet of the NOx absorption unit.
  • the NOx absorbing unit comprises a denitration reactor and a NOx fixed nutrient stream dispenser.
  • the optical density value was measured by a spectrophotometer, and the absorbance of the algae liquid at a wavelength of 680 nm was measured using distilled water as a control, as an index of the microalgae concentration.
  • the ICS3000 ion chromatograph (Dionex, USA) was used to determine the NO 3 - content or NO 2 - content in the aqueous solution.
  • the instrument was equipped with an EG40 eluent automatic generator, a conductivity detector and a chameleon chromatography workstation; IonPac AS11-HC type separation column (250mm ⁇ 4mm id); IonPac AG11 type protection column (50mm ⁇ 4mm id); ASRS-ULTRA anion self-suppressor.
  • Eluent KOH solution; flow rate 1 mL/min; eluent concentration: 30 mmol/L; injection volume 60 ⁇ L; column temperature 30 ° C; inhibition current 100 mA; external standard method peak area quantification.
  • Bacterial Count follows the steps below for bacterial count
  • Sample washing Pipette 1 ml sample and wash 2-3 times with 1 ⁇ PBS; 2. Preliminary separation: According to the difference of centrifugal force of algae and bacteria, firstly centrifuge with 2 rpm for 2 min to separate algae (bacteria in supernatant, algae Precipitation); if the algae content is high, repeat again; 3. Collect the supernatant, the amount of algae in the supernatant is negligible, centrifuge at 8000 rpm for 5 min, Discard the supernatant; 4. Resuspend the pellet with 500ul bacterial rupture agent, react at room temperature for 15min; centrifuge at 5.8000rpm for 5min, wash the bacterial solution twice with 1 ⁇ PBS; 6.
  • Bacterial density in the measured solution count result / 4 ⁇ dilution factor ⁇ 4 ⁇ 10 4 / ml
  • Microalgae culture medium The composition of the medium is shown in Tables 1 to 5.
  • the denitration activity refers to the mole fraction of the NOx content of the industrial waste gas after treatment to the NOx content of the industrial waste gas before the treatment.
  • This example is used to illustrate "the effect of adding EM bacteria on the self-cultivation of microalgae light energy".
  • BG11 medium add nutrients according to Table 1, the medium is not sterilized
  • the medium is not sterilized
  • the temperature between 20 ⁇ 30 °C
  • pass compressed air and CO 2 culture when the algae PH> 10 ventilation of CO 2
  • the CO 2 was stopped when the algae solution PH ⁇ 7.5.
  • natural daylight culture is used to control the daytime light intensity up to 60,000 lux.
  • the OD 680 value of the algae liquid is measured every day, and the harvest is continued after 14 days of continuous culture.
  • the mixture containing CO 2 is stopped 1 day before the end of the culture, and the culture is terminated. Thereafter, the algal mud and the culture residue are obtained by centrifugation.
  • the growth curve of microalgae is shown in Fig. 1. The two tests in Fig.
  • Examples 2 to 5 are for explaining "the influence of the amount of EM bacteria added on the culture of microalgae in the light energy conservation".
  • the chlorella was cultured by using BG11 medium (the nutrient was added according to Table 1, and the medium was not sterilized), and 2 g/L of glucose was added during the culture, and the temperature was controlled between 20 and 30 ° C, and compressed air and CO were introduced.
  • 2 culture when the algae liquid PH>10, the CO 2 is introduced , and when the algae liquid is pH ⁇ 7.5, the CO 2 is stopped.
  • natural daylight culture is used to control the daytime light intensity up to 60,000 lux, and the OD 680 value of the algae liquid is measured every day.
  • the growth curve of the microalgae is shown in Fig. 2.
  • the EM addition amount is 3.6 ⁇ 10 6 /L algae liquid
  • the bacteria count of the algae liquid in the culture process is ⁇ 8 ⁇ 10 6 /mL algae liquid
  • the harvest is continued after 14 days of continuous culture, and the CO is stopped 1 day before the end of the culture.
  • 2 flue gas, and the pH of the algae liquid is naturally raised to 9.4, then the culture is ended, and the algae mud and the culture residue are obtained by centrifugation.
  • Embodiment 2 This embodiment is basically the same as Embodiment 2 except that the EM addition amount is 1.8 ⁇ 10 7 /L algae liquid. After the addition of EM, the bacterial count of the algal liquid was monitored ⁇ 1 ⁇ 10 7 /mL algae liquid after the system reached steady state during the culture process, and the pH of the algae liquid was naturally raised to 9.3 at the end of the culture. The growth curve of microalgae is shown in Figure 2.
  • Embodiment 2 This embodiment is basically the same as Embodiment 2 except that the EM addition amount is 3.6 ⁇ 10 7 /L algae liquid. After the addition of EM, the bacterial count of the algae liquid was monitored ⁇ 2 ⁇ 10 7 /mL algae liquid after the system reached steady state during the culture process, and the pH of the algae liquid was naturally raised to 8.9 at the end of the culture. The growth curve of microalgae is shown in Figure 2.
  • Embodiment 2 This embodiment is basically the same as Embodiment 2 except that the EM addition amount is 7.2 ⁇ 10 7 /L algae liquid.
  • the EM addition amount is 7.2 ⁇ 10 7 /L algae liquid.
  • the bacterial count of the algae liquid was monitored ⁇ 5.8 ⁇ 10 7 /mL algae liquid, and the pH of the algae liquid was naturally raised to 8.7 at the end of the culture.
  • the growth curve of microalgae is shown in Figure 2.
  • This comparative example is basically the same as Example 2 except that EM bacteria are not added.
  • the bacterial count of the algae solution during the culture process was up to 1.2 ⁇ 10 8 /mL algae liquid, and the pH of the algae liquid was naturally raised to 7.9 at the end of the culture.
  • the growth curve of microalgae is shown in Figure 2.
  • Examples 6-8 are used to illustrate "metabolism of nitrate and nitrite by microalgae".
  • BG11 medium add nutrients according to Table 1, the medium is not sterilized
  • the medium is not sterilized
  • control the temperature between 20 ⁇ 30 °C pass compressed air and CO 2 culture, when the algae PH> 10 ventilation of CO 2, the CO 2 was stopped when the algae solution PH ⁇ 7.5.
  • natural daylight culture is used to control the daytime light intensity up to 60,000 lux, and the OD 680 value of the algae liquid is measured every day for 14 days.
  • the growth curve of microalgae is shown in Figure 3.
  • This example is basically the same as Example 6, except that 1.5 g/L of sodium nitrate in the medium was replaced with 1.35 g/L of sodium nitrite and 0.15 g/L of sodium nitrate. See the growth curve of microalgae image 3.
  • This embodiment is basically the same as Example 7, except that the cultured microalgae is a single needle algae.
  • the growth curve of microalgae is shown in Figure 3.
  • Fig. 3 It can be seen from Fig. 3 that the selected microalgae species can be grown well using both nitrate and nitrite.
  • Examples 9 to 16 are for explaining "the effect of EM bacteria on the metabolism of inorganic nitrogen sources by microalgae in the case where a large amount of organic carbon source is added".
  • the chlorella was cultured by using BG11 medium (the nutrient was added according to Table 1, and the medium was not sterilized); when the OD 680 value was 4, the nutrient composition of the heterotrophic medium was supplemented with the amount specified in Table 4.
  • the control temperature is between 20 and 30 ° C, and the compressed air is introduced into the CO 2 culture.
  • the algae liquid has a pH of >10, the CO 2 is introduced , and when the algae liquid is at pH 7.5, the CO 2 is stopped.
  • the pH value of the algae liquid is 8.6, and the algal mud and the culture residue are obtained by centrifugation.
  • the total content of NO 3 - and NO 2 - in the culture residue was analyzed ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 4.
  • This embodiment is basically the same as Example 9, except that the cultured microalgae is a single needle algae.
  • the bacterial count of the algae liquid was up to 4.6 ⁇ 10 7 /mL algae liquid, and the pH of the algae liquid was naturally increased to 8.2 at the end of the culture, and NO 3 - and NO 2 in the culture residue were analyzed .
  • the total content is ⁇ 200 ⁇ g / g.
  • the growth curve of microalgae is shown in Figure 4.
  • This embodiment is basically the same as Embodiment 9, except that the first aspect is that the amount of EM bacteria added is 7.9 ⁇ 10 7 /L algae liquid, and the second EM bacteria are not added; and the second addition is The amount of glucose was 30 g/L, and no third glucose was added.
  • the bacterial count of the algae liquid during the breeding process was up to 2.6 ⁇ 10 7 /mL algae liquid.
  • the pH of the algae liquid was naturally raised to 8.2 at the end of the culture, and the NO 3 - and NO 2 - in the culture residue were analyzed. The total content is ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 4.
  • This embodiment is basically the same as that of the embodiment 11, except that the cultured microalgae is a single needle algae.
  • the bacterial count of algae was up to 5.2 ⁇ 10 7 /mL algae in the culture process.
  • the pH of the algae liquid was naturally increased to 7.8 at the end of the culture, and NO 3 - and NO 2 in the culture residue were analyzed .
  • the total content is ⁇ 200 ⁇ g / g.
  • the growth curve of microalgae is shown in Figure 4.
  • This comparative example is basically the same as that of Example 9, except that EM bacteria are not added.
  • the bacterial count of the algae liquid during the monitoring was as high as 13.6 ⁇ 10 8 /mL algae liquid, and the pH of the algae liquid was naturally raised to 7.2 at the end of the culture.
  • the growth curve of microalgae is shown in Figure 4.
  • the chlorella was cultured by using BG11 medium (the nutrient was added according to Table 1, and the medium was not sterilized); when the OD 680 value was 4, the nutrient composition of the heterotrophic medium was supplemented with the amount specified in Table 4.
  • the control temperature is between 20 and 30 ° C, and the compressed air is introduced into the CO 2 culture.
  • the algae liquid has a pH of >10, the CO 2 is introduced , and when the algae liquid is at pH 7.5, the CO 2 is stopped.
  • natural daylight culture is used to control the daytime light intensity up to 60,000 lux.
  • the chlorella is first cultivated under light autotrophic conditions for 2 days, then 2 g/L glucose is added, and 1.8 ⁇ 10 8 / EM bacteria were added to the amount of L-algae solution, and the OD 680 value of the algae solution was measured every day; after 3 days of culture, 10 g/L of glucose was added again, and EM bacteria were added according to 1.8 ⁇ 10 8 /L algae solution; Adding glucose 10g/L, the bacterial count of the algae solution during the breeding process is up to 2.9 ⁇ 10 7 /mL algae liquid, harvested after 14 days of continuous culture, and the CO 2 is stopped after the last addition of glucose, and the algae PH is stopped when the culture is finished.
  • the value was 9.2, and the algal mud and culture residue were obtained by centrifugation.
  • the total content of NO 3 - and NO 2 - in the culture residue was analyzed ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 5.
  • This example is basically the same as Example 13 except that the second aspect of EM bacteria is not added; and the amount of glucose added for the second time is 30 g/L, and no third glucose is added.
  • the bacterial count of the algae solution during the breeding process was up to 2.9 ⁇ 10 7 /mL algae liquid.
  • the pH of the algae liquid was naturally raised to 9.3 at the end of the culture, and the NO 3 - and NO 2 - in the culture residue were analyzed. The total content is ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 5.
  • This example is basically the same as Example 13, except that NaNO 3 is replaced with KNO 3 in BG11 medium, and the amount of KNO 3 added is 0.5 g/L.
  • the bacterial count of the algae liquid during the culture process was up to 1.3 ⁇ 10 7 /mL algae liquid, and the pH value of the algae liquid at the end of the culture was 9.4, and the total content of NO 3 - and NO 2 - in the culture residue was analyzed. ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 5.
  • This example is basically the same as Example 14, except that NaNO 3 in BG11 medium is replaced with KNO 3 and KNO 3 is added in an amount of 0.5 g/L.
  • the bacterial count of the algae liquid during the culture process was up to 1.7 ⁇ 10 7 /mL algae liquid, and the pH value of the algae liquid at the end of the culture was 9.3, and the total content of NO 3 - and NO 2 - in the culture residue was analyzed. ⁇ 10 ⁇ g/g.
  • the growth curve of microalgae is shown in Figure 5.
  • EM bacteria promotes the growth of microalgae using potassium nitrate or sodium nitrate as a nitrogen source.
  • Examples 17 to 18 are for explaining "the case where the NOx is fixed by the culture residue obtained by the cultured algae and the microalgae is continuously cultured with the solution after fixing the NOx".
  • O 3 is used to absorb NOx.
  • the mixture of NO 2 and NO is used to simulate the actual flue gas, the compressed air is used as the carrier gas, the NOx flow rate is 0.3L/min, and the O 3 -containing gas comes from the XM-Y mobile ozone generated by Qingdao Xinmei Purification Equipment Co., Ltd.
  • the flow rate is 1 L/min.
  • the total flow rate is 150 L/h.
  • the NOx concentration of the inlet and outlet gases is measured, and the NOx fixed rate is calculated by the following formula;
  • NOx fixing rate (1 - outlet NOx concentration / inlet NOx concentration) ⁇ 100%;
  • the total concentration of NOx at the inlet is basically stable at 620 mg/m 3 (wherein the NO content is about 600 mg/m 3 and the NO 2 content is about 20 mg/m 3 ).
  • the flow chart is shown in Fig. 6.
  • the absorption tower has a diameter of 100 mm and a height of 700 mm.
  • the bottom of the tower is provided with a mesh-shaped gas distributor in which 3 L of the culture residue produced in Example 16 is contained.
  • the NOx mixed gas was directly introduced into the absorption tower, and the operation was stopped for 22 hours, and the culture residue in the alkali column was taken out, and the total content of NO 3 - and NO 2 - was determined to be 5900 ⁇ g / g.
  • Microalgae are cultured using NOx fixative.
  • the above NOx fixative was used as the microalgae culture medium, and other nutrients other than the nitrogen source were supplied in BG11 medium, and the chlorella was cultured.
  • the rest of the culture method was the same as in Example 16.
  • the bacteria count in the algae was monitored during the breeding process. It was 1.8 ⁇ 10 7 /mL algae liquid, and it was harvested after 14 days of continuous culture. After the last addition of glucose, the CO 2 was stopped. When the culture was finished, the pH value of the algae liquid was 9.1, and the algal mud and the culture residue were obtained by centrifugation.
  • the total content of NO 3 - and NO 2 - in the culture residue was analyzed ⁇ 10 ⁇ g / g. It can be seen from Fig.
  • the nutrient solution with fixed NOx is used as the culture nutrient solution, and the growth of microalgae can be promoted by adding EM bacteria.
  • NO 3 - and NO 2 - in the algae solution are fixed and returned to alkaline, so that it can be further used as an alkaline fixing solution for denitration of exhaust gas.
  • the NOx was fixed in the same manner as in Example 17 except that the absorption column was filled with the 3 L culture residue obtained in Example 10. After fixing for 22 hours, the culture residue in the alkali column was taken out, and the total content of NO 3 - and NO 2 - was measured to be 5800 ⁇ g / g.
  • Microalgae are cultured using NOx fixative.
  • the above NOx fixative was used as the microalgae culture medium, and other nutrients other than the nitrogen source were provided in BG11 medium, and the single needle algae were cultured.
  • the rest of the culture method was the same as in the example 10, and the bacterial count of the algae liquid was monitored during the breeding process. It was 9.2 ⁇ 10 6 /mL algae liquid, and it was harvested after continuous culture for 8 days. After the last addition of glucose, the CO 2 flue gas was stopped. When the culture was finished, the pH value of the algae liquid was 8.7, and the algae mud and the culture residue were obtained by centrifugation. The total content of NO 3 - and NO 2 - in the culture residue was analyzed ⁇ 200 ⁇ g / g.
  • Example 19 is used to illustrate "the effect of EM bacteria on the photo-heterotrophy of microalgae".
  • Example 9 This example is basically the same as Example 9, except that it is cultured in the absence of light.
  • the pH of the algal solution at the end of the culture was measured to be 7.7.
  • the growth curve of microalgae is shown in Figure 9.
  • This comparative example is used to illustrate "fixed assimilation of NOx by EM bacteria".
  • This comparative example is basically the same as that of Example 9, except that it is only in the following aspects: EM bacteria are simply cultured; the medium is sterilized before culture; the medium is still BG11 (Table 1), but the initial concentration of NO 3 - is 6900 ug. /g; cultured for 14 days. The total content of NO 3 - and NO 2 - at the end of the analysis was 5600 ug/g. It can be seen that the rate of consumption of inorganic nitrogen sources by EM bacteria during growth is much lower than that of microalgae.
  • This example is intended to illustrate the immobilization of NOx with an alkaline culture residue.
  • the alkaline culture residue of Example 14 was taken as 3 L; the potassium and sodium ion concentrations in the alkaline culture residue were analyzed, and 3 L of an aqueous solution having the same potassium ion concentration and sodium ion concentration was prepared, and the paired anion was HCO 3 - and CO. 3 2- , the pH of the prepared aqueous solution was 9.27, which was substantially the same as the pH of the alkaline culture residue of Example 14.
  • the NOx was fixed by the method of Example 17 using the above-mentioned alkaline culture residue and the prepared aqueous solution as fixing liquids respectively, and the fixed efficiency curve for NOx is shown in FIG.
  • This comparative example is used to illustrate the effect of culturing chlorella with a low concentration of NH 4 HCO 3 .
  • Chlorella was cultured in BG11 medium (Table 1), and the nitrogen source in BG11 medium was changed to NH 4 HCO 3 .
  • the concentration of nitrogen source was 3.3 mmol/L.
  • the concentration of nitrogen source was much lower than that in BG11 medium.
  • the initial concentration of the algae was OD 680 of 0.5, and it was cultured in compressed air at a controlled temperature of 20 to 30 °C. Natural daylight culture is used during the cultivation process to control daytime light intensity up to 60,000 lux. Its growth curve is shown in Figure 1.
  • This comparative example is used to illustrate the effect of culturing chlorella with low concentrations of NaNO 3 .
  • This comparative example is used to illustrate the effect of culturing chlorella with very high concentrations of NaNO 3 .
  • This example is intended to illustrate the effect of the present invention in the self-cultivation of chlorella.
  • This example is basically the same as Comparative Example 4, except that the nitrogen source and its concentration are still in the formulation of BG11 medium.
  • the pH value is higher than 10 in the later stage of cultivation, the pH is adjusted to a suitable range by supplementing nitric acid.
  • the OD 680 value of the algae solution was measured daily, and the growth curve is shown in Fig. 1.
  • This example is intended to illustrate the effect of the present invention in the self-cultivation of spirulina.
  • Spirulina was cultured in Z-culture medium (Table 3).
  • the initial concentration of algae was OD 680 of 0.3, and it was cultured in compressed air.
  • the temperature was controlled between 20 and 30 ° C.
  • the pH was higher than 10.5, the nitric acid was added.
  • the pH is adjusted within the appropriate range.
  • Natural daylight culture is used during the cultivation process to control daytime light intensity up to 60,000 lux.
  • the OD 680 value of the algae solution was measured daily, and the growth curve is shown in Fig. 2.
  • This example is intended to illustrate the effect of the present invention in the simultaneous cultivation of chlorella (no sterilization operation).
  • This example is basically the same as the same as Comparative Example 4 except that the chlorella heterotrophic medium (Table 4) is used, and 2 g/L of glucose and 5 ⁇ 10 7 of EM bacteria are added every three days during the culture. L-algae solution, when the pH is higher than 10, the nitric acid is added to adjust the pH within a suitable range. The OD 680 value of the algae solution was measured daily, and the growth curve is shown in Fig. 1.
  • This example is intended to illustrate the effect of the present invention in the simultaneous cultivation of spirulina (no sterilization operation).
  • This embodiment is basically the same as the embodiment 21 except that: during the cultivation process, 2 g/L of glucose and 5 ⁇ 10 7 /L of EM bacteria are added every three days, and when the pH value is higher than 10.5, the supplement is added. Nitric acid adjusts the pH to a suitable range. The OD 680 value of the algae solution was measured daily, and the growth curve is shown in Fig. 2.
  • This example is intended to illustrate the effect of the present invention in the sterile heterotrophic culture of Chlorella.
  • Chlorella was basically the same as in Comparative Example 4, and heterotrophic culture was carried out using a chlorella heterotrophic culture medium (Table 4).
  • the initial concentration of the algae was OD 680 of 0.5, and compressed air was introduced in a sterile, matt state. Culture, control temperature between 20 ⁇ 30 ° C. When the glucose consumption is exhausted, glucose 10g/L is added in time; when the pH is higher than 10, the supplemental nitric acid adjusts the pH within a suitable range.
  • the OD 680 value of the algae solution was measured daily, and the growth curve is shown in Fig. 1.
  • the growth efficiency of the microalgae can be improved by the method of the present invention. If a large amount of nitrate is added at the beginning of the culture, the high concentration of nitrate does not significantly promote the growth of the microalgae.
  • This example is intended to illustrate the effect of changes in the concentration of nitric acid or H 2 O 2 on the rate of decomposition of hydrogen peroxide.
  • Table 6 shows that both the increase in the concentration of nitric acid and the increase in the concentration of hydrogen peroxide result in a significant increase in the loss of hydrogen peroxide.
  • This example is intended to illustrate the denitration effect of the present invention on low concentration NOx.
  • the simulated exhaust gas was prepared with NO, NO 2 and nitrogen, the concentration of NO was 500 ppm by volume, and the concentration of NO 2 was 20 ppm by volume.
  • the absorption liquid consists of 15 m% nitric acid, 0.4 m% hydrogen peroxide and the balance water.
  • the absorption device adopts a glass tower, the glass tower has a diameter of 100 mm and a height of 700 mm; a sieve plate is arranged at the bottom of the glass tower, the sieve plate has a pore diameter of 16 ⁇ m to 30 ⁇ m; the tower is filled with 3000 ml of absorption liquid; and the flow rate of the simulated exhaust gas is 150 L/h;
  • the test was carried out at normal temperature and normal pressure. The test results are shown in Table 7. (Measured by the method of GB/T14642-2009, it is found that there is no nitrite in the absorption liquid after the test)
  • Table 7 shows that in the initial stage of denitration, the denitrification activity of the absorption liquid is very low. With the increase of time, the denitration activity of the absorption liquid slowly increases continuously. After 16 hours, the denitration activity of the absorption liquid enters a stable period, and the denitration rate reaches 90% or more. .
  • This example is intended to illustrate the denitration effect of the present invention on low concentration NOx.
  • Example 26 This example is basically the same as Example 26 except that the concentration of hydrogen peroxide is 1 m% and the concentration of nitric acid is 25 m%.
  • the test results are shown in Table 8. (Measured by the method of GB/T14642-2009, it is found that there is no nitrite in the absorption liquid after the test)
  • This embodiment is for explaining the denitration effect of high concentration NOx when the single tower is used in the present invention.
  • This embodiment is basically the same as the embodiment 26 except that the concentration of hydrogen peroxide is 0.3 m%, the concentration of nitric acid is 15 m%, and the concentration of NO in the simulated exhaust gas is 3200 ppm (volume), the concentration of NO 2 . It is 100 ppm by volume.
  • the test results are shown in Table 9. (Measured by the method of GB/T14642-2009, it is found that there is no nitrite in the absorption liquid after the test)
  • This comparative example is used to illustrate the denitration effect when high concentration H 2 O 2 is used.
  • Example 26 This example is basically the same as Example 26 except that the concentration of hydrogen peroxide is 2.5 m% and the concentration of nitric acid is 15 m%.
  • the test results are shown in Table 10.
  • This embodiment is intended to illustrate the acid process flow when the system of the present invention is employed.
  • a mixed gas containing 480 ppm of NO and remaining air first enters the denitration reactor 1-1 (aqueous solution containing 0.5% hydrogen peroxide and 15% dilute nitric acid) to obtain a dilute nitric acid, yield of nitric acid.
  • the purified purge gas C was vented.
  • the microalgae nutrient solution E 3kg is sent to the NOx fixed nutrient stream distributor 1-2 (the nutrient solution is Z-culture medium + 10g/L NaNO3), mixed with the culture residue F and dilute nitric acid, and then sent to the microalgae culture.
  • the flow rate of 2 is 200 L/h.
  • the pH of the algae liquid is ⁇ 8.5
  • the CO 2 is stopped.
  • the pH of the algae liquid is >10.5, the CO 2 is continuously supplied, and the light intensity is 10,000 lux.
  • the algae liquid is sent to the microalgae filter separator 3 for filtration separation, and the obtained culture residue F2.5kg is returned to the NOx fixed nutrient stream distributor 1-2 for circulation culture.
  • the concentrated algae G 250g was sent to the microalgae dryer 4 and dried to obtain 25 g of the microalgae product.

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Abstract

提供了一种养殖微藻与工业废气脱硝联合的方法及用于该方法的系统。联合方法包括以下步骤：（1）养殖微藻的养殖步骤；（2）将步骤（1）收获的藻液分离为湿微藻（藻泥）和养殖残液的分离步骤；（3）用从步骤（2）获得的养殖残液完成对工业废气脱硝的NOx吸收固定步骤；其中，将从步骤（3）获得的固定了NOx的营养物流为步骤（1）的微藻养殖提供氮源。在所述养殖微藻的过程中，向藻液中加入EM菌。微藻优选是小球藻、栅藻、单针藻或螺旋藻。系统包含，任选从上游到下游地：NOx固定单元；微藻养殖器；分离器；和循环线路，用于将来自分离器的养殖残液循环回工艺上游。

Description

养殖微藻与工业废气脱硝联合的方法及用于该方法的系统 技术领域
本发明涉及一种养殖微藻的方法和一种养殖微藻与工业废气脱硝联合的方法。
背景技术
能源与环境是人类社会可持续发展所面临的重要课题。一方面，支撑人类现代文明的化石能源不可再生，开发替代能源迫在眉睫；另一方面，利用化石能源时所产生的废气与污水，已经对环境造成了严重的影响，这些问题需要有统筹协调的解决方案。
微藻是种类繁多且分布极广的水生低等植物，它们通过高效的光合作用，将光能转化为脂肪或淀粉等碳水化合物的化学能，被誉为“阳光驱动的活化工厂”。利用微藻生产生物能源和化学品有望同时达到替代化石能源和净化废气与污水的双重目的。
自然界中，微藻与细菌之间存在着复杂的生态关系，一些特定的微藻和细菌之间可能相互促进，而另一些之间又可能相互抑制。养殖微藻的一个已知的困难是，水和空气中存在大量的有害细菌，这些有害细菌不利于微藻的生长，严重时会导致养殖失败。采用开放体系养殖微藻时，不可能实现无菌状态，被细菌污染的风险较高；采用封闭的养殖体系并进行严格的灭菌可实现无菌状态，然而对于大规模养殖微藻而言，这种方法的成本过于昂贵。
工业废气中的氮氧化物(NOx)是主要的大气污染物之一，其不仅会产生光化学烟雾和酸雨，还会导致严重的温室效应，是大气雾霾的主要诱因，因此工业废气的脱硝问题日益受到人们的重视。工业废气的脱硝方法可分为干法和湿法两种。催化还原法(SCR)与非催化还原法(SNCR)是常用的干法脱硝方法，这两种方法的投资和运行成本较高，并且将NOx还原成了低价值的氮气，没有达到资源化利用NOx的目的。湿法脱硝是将废气中的NOx吸收固定于吸收液中的方法，此类方法的投资和运行成本低，但需要解决两方面的问题，一是工业废气中的NOx主要是NO(一般占90％以上)，而NO极难溶于水，因此需要采取措施来解决NO的溶解度问题；二是吸收过程中难免生成亚硝酸或亚硝酸盐，而亚硝酸或亚硝酸盐是剧毒性物质，因此需要采取措施解决其分离、利用或处理问题。
另一方面，氮是微藻生长过程中消耗最快、最易缺乏的营养元素之一。 大量消耗的氮肥对养殖微藻而言是昂贵的。因此，如果能将养殖微藻与工业废气脱硝结合起来，一方面可以利用NOx为微藻生长提供氮肥，从而降低养殖微藻的成本；另一方面又可以净化废气、减少NOx的排放，产生更大环境效益。已有一些文献公开了“将工业废气直接通入微藻养殖器进行脱硝方法”，然而这些方法均存在以下难以解决的问题：①利用微藻进行工业废气脱硝必须解决限制其商业化的一些问题，比如养殖微藻需要光照和温暖的气候条件，而天气变化必然导致微藻脱硝效率的变化，“直接通入工业废气”将难以匹配废气排放工况与微藻养殖工况，造成两段工艺互相影响，无法满足实际生产的减排要求；②一氧化氮(NO)是NOx的主要成分，而NO在水中的溶解度极低，因此“直接通入工业废气”无法解决NOx中大量NO不溶于水而难以吸收的问题。
化工工业所产生的NOx数量巨大，如果要用微藻固定工业废气中的NOx，就需要使微藻固定NOx的速率与工业排放NOx的速率相匹配，并尽量减少微藻培养装置的占地面积。通常，光能自养的效率小于30g.m-2.d-1，室外大规模培养的效率一般低于10g.m-2.d-1，以这样的效率进行工业废气脱硝会占用大量的土地，因此有必要进一步提高微藻的养殖效率。添加有机碳源进行异养培养或光能兼养是加速微藻生长的可行方法，然而在添加有机碳源后，藻液极易遭受有害细菌的污染，导致细菌的生长显著快于微藻的生长，从而导致微藻养殖失败。
规模化养殖微藻需要大量的水，如果不对其进行循环利用，则会大大增加养殖成本。已知大多数微藻不能适应高浓度的铵盐溶液，比如硫铵在现有技术中常常被用作微藻的抑制剂；而用硝盐为微藻提供氮源，将难以对养殖用水循环利用，原因在于金属离子会在养殖水体中不断累积，导致其盐度逐渐升高，而高盐度通常对微藻的生长有明显的抑制作用。
发明内容
本发明的第一个目的是提高微藻的养殖效率，特别是提高异养培养和光能兼养的养殖效率。本发明的第二个目的是避免异养培养和光能兼养时的无菌操作。本发明的第三个目的是将微藻养殖与工业废气脱硝有机地结合起来，既能够利用NOx为微藻生长提供氮源，又能避免因废气排放与微藻养殖工况不同而造成的相互影响。本发明的第四个目的是，用硝酸/ 过氧化氢的水溶液作为吸收液对工业废气脱硝，以避免生成有毒的亚硝酸；同时提高该过程的过氧化氢利用率。
具体而言，本发明包括例如以下方面的内容。
一方面，本发明提供了一种高效养殖微藻的方法，其特征在于，养殖过程中，向藻液中加入EM菌。
另一方面，本发明提供了一种养殖微藻的方法，其中在养殖微藻的培养基中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供；其特征在于，养殖过程中，用硝酸和/或亚硝酸调节藻液的pH值。
另一方面，本发明提供了一种养殖微藻和工业废气脱硝的联合方法，包括以下步骤：
(1)养殖微藻的养殖步骤；
(2)将步骤(1)收获的藻液分离为湿微藻(藻泥)和养殖残液的分离步骤；
(3)用从步骤(2)获得的养殖残液完成对工业废气脱硝的NOx固定步骤；和
(4)任选地，将步骤(2)获得的藻泥干燥以得到微藻产品的干燥步骤；
其中，将从步骤(3)获得的固定了NOx的营养物流为步骤(1)的微藻养殖提供氮源。
上述步骤(3)可通过各种方式实施。
在一个优选实施方案中，所述联合方法涉及酸法工艺，其中所述步骤(3)包括：
(i)将工业废气中的NOx转化为硝酸和/或亚硝酸的步骤；和
(ii)将步骤(2)得到的养殖残液与步骤(i)中获得的硝酸和/或亚硝酸(优选硝酸和可选的亚硝酸)混合，从而实现对工业废气的脱硝。
在该实施方案中，用该混合得到的溶液作为所述固定了NOx的营养物流来为步骤(1)的微藻养殖过程提供氮源。
在另一个优选实施方案中，所述联合方法涉及碱法工艺，其中所述步骤(3)包括：
(i′)用步骤(2)得到的养殖残液直接固定工业废气中的NOx。
在该实施方案中，用通过该步骤(i′)得到的该固定了NOx的营养物流为步骤(1)的养殖微藻过程提供氮源。
另一方面，本发明提供了用于养殖微藻和工业废气脱硝的联合方法的系统，其包含，任选从上游到下游地：
NOx固定单元，用于进行脱硝反应并提供固定了NOx的营养物流；
微藻养殖器，用于利用所述固定了NOx的营养物流进行微藻养殖；
分离器，用于将从微藻养殖器收获的藻液分离为藻泥和养殖残液；和
循环线路，用于将来自所述分离器的养殖残液循环回工艺上游，用于固定工业废气中的NOx；
以及任选地，干燥器，用于干燥所述藻泥以得到微藻产品。
在一个优选实施方案中，所述NOx固定单元具有含NOx工业废气入口、养殖残液入口、固定了NOx的营养物流出口和净化后的工业废气出口，以及任选地营养液入口。
在一个优选实施方案中，所述微藻养殖器具有固定了NOx的营养物流入口、藻种入口和藻液出口，以及任选地营养液入口和任选地EM菌入口。
在一个优选实施方案中，所述分离器具有藻液入口、藻泥出口和养殖残液出口。
在一个优选实施方案中，所述循环线路连接分离器的养殖残液出口和NOx固定单元的养殖残液入口。
优选地，在酸法工艺中，所述NOx固定单元或微藻养殖器具有营养液入口。
优选地，在碱法工艺中，所述微藻养殖器具有营养液入口。
在一个优选实施方案中，所述联合方法涉及酸法工艺，其中所述NOx固定单元包含脱硝反应器和NOx固定营养物流配制器。
在一个优选实施方案中，所述联合方法涉及碱法工艺，其中所述NOx固定单元为脱硝反应器。
在一个优选实施方案中，在养殖微藻的培养基中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供。在一个优选实施方案中，养殖过程中，用硝酸和/或亚硝酸调节藻液的pH值。
在一个优选实施方案中，在养殖微藻的培养基中，氮源以碱金属硝酸盐和/或碱金属亚硝酸盐的形式提供。
在一个优选实施方案中，微藻的养殖方式为异养培养或光能兼养。
进一步地，在一个优选实施方案中，当微藻的养殖方式为异养培养或光能兼养时，所使用的有机碳源选自糖、有机酸、有机酸盐、醇、纤维素水解物和与淀粉水解物中的至少一种；优选葡萄糖、果糖、乙酸、乙酸钠、乳酸、乙醇、甲醇和纤维素水解物中的至少一种，更优选葡萄糖。
进一步地，在一个优选实施方案中，当微藻的养殖方式为异养培养或光能兼养时，所使用的有机碳源的浓度控制在1g/L藻液～30g/L藻液，优选控制在2g/L藻液～10g/L藻液。
在一个优选实施方案中，养殖方式为光能自养或光能兼养，光强为1000～200000勒克斯。
在一个优选实施方案中，本发明所述养殖微藻的方法还包括从收获的藻液中分离出藻泥，并将分离出藻泥后获得的养殖残液循环用于养殖微藻的步骤。特别地，现有技术认为在微藻养殖中使用硝酸盐足以作为氮源，但一些情况下硝酸盐所含金属离子的累积可能会抑制藻生长。在本发明中，当采用酸法工艺时，无需额外加入硝酸盐，也就不会向工艺中引入新的金属阳离子，因而不会造成金属阳离子在工艺中的累积。
在一个优选实施方案中，在微藻的养殖过程中，向藻液中加入EM菌。M菌的加入量为1×105个/L藻液～9×108个/L藻液，优选为1×106个/L藻液～5×108个/L藻液，进一步优选为1×106个/L藻液～1×108个/L藻液。。
在一个优选实施方案中，在所述联合方法的步骤(i)中，采用湿法脱硝将工业废气中的NOx转化为硝酸。在一个优选实施方案中，湿法脱 硝中用于吸收NOx的吸收液由0.5m％～58m％的硝酸、0.001m％～25m％的过氧化氢和余量水组成。
在一个优选实施方案中，在所述湿法脱硝中，吸收液由10m％～25m％的硝酸、0.1m％～1m％的过氧化氢和余量水组成。
本发明取得了如下的技术效果。
根据本发明，在养殖微藻的过程中，用硝酸和/或亚硝酸调节藻液的pH值，大大提高了养殖微藻的效率。
根据本发明，微藻养殖与工业废气脱硝是两个相对独立的过程，避免了因废气排放与微藻养殖工况不同而造成的相互影响，避免了大量NO不溶于水而难以固定的问题，不需要额外的碱液就能利用工业废气中的NOx为微藻提供氮源，这使得本发明的方法养殖成本更低。
本发明避免了金属离子的累积问题，使养殖水体得以循环利用。
根据本发明，在藻液中加入EM菌，能够有效地抑制有害细菌的繁殖，大幅度提高微藻的生长速率。这一特点使本发明在异养培养或光能兼养时，不需要进行消毒灭菌，因此使本发明具有更大的优势。
根据本发明，采用低浓度过氧化氢和低浓度硝酸的水溶液作为吸收液对工业废气脱硝，过氧化氢的分解率更低、有效利用率很高。
根据本发明，在对工业废气脱硝的同时生产稀硝酸，该稀硝酸中不含有毒的亚硝酸，更有利于将其用作养殖微藻的氮源。
附图说明
图1为光能自养的微藻生长曲线。
图2为光能兼养的微藻生长曲线。
图3为以硝盐为氮源的微藻生长曲线。
图4、图5为添加大量有机碳源的微藻生长曲线。
图6为NOx固定工艺的示意图。
图7、图8为以固定了NOx的营养物流为氮源的微藻生长曲线。
图9为无光异养的条件下，添加EM菌的微藻生长曲线。
图10为NOx固定率随时间的变化曲线。
图11为不同条件下小球藻生长曲线。
图12为不同条件下螺旋藻生长曲线。
图13为按照本发明的联合方法的总的工艺流程示意图。
图14为按照本发明的联合方法的酸法工艺流程示意图。
图15为按照本发明的联合方法的酸法工艺结合附加的光能自养的流程示意图。
在这些图中：
1：NOx固定单元；
1-1：脱硝反应器；
1-2：NOx固定营养物流配制器
2：微藻养殖器；
3：分离器；
4：干燥器；
5：CO2吸收营养物流配制器；
6：CO2微藻养殖器；
7：CO2微藻养殖分离器
A：含NOx的气体；
B：固定了NOx的营养物流；
C：净化后的气体；
D：藻种；
E：营养液；
F：养殖残液；
G：湿微藻；
H：微藻产品。
I：CO2吸收微藻营养液；
J：CO2吸收营养物流；
K：CO2吸收藻种；
L：CO2；和
M：CO2养殖藻液。
具体实施方式
以下详细说明本发明的具体实施方式，但是需要指出的是，本发明的保护范围不受这些具体实施方式的限制，而是由权利要求书来确定。
除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
在本发明中，例如，培养基是指微藻养殖过程中，供微藻在其中生长的水体，其中已包含对微藻生长而言的所有必要营养物质，除非另有指明。
在本发明中，例如，营养物流是指含有一种或多种营养源比如氮源、磷源或碳源、用于配制成营养基的物流，除非另有指明。
在本发明中，例如，藻液是将微藻加入培养基之后所形成的体系，除非另有指明。
在本发明中，当技术方案以“包含”、“包括”所列举的某些要素等开放式限定的形式给出时，本领域技术人员将理解的是，由这些要素构成、或者基本上由这些要素构成的实施方式显然能够用于实施所述技术方案。因此，本领域技术人员理解的是，本发明中以所述开放式限定给出的技术方案也涵盖由列举要素构成、或者基本上其构成的具体实施方式。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
本发明所公开的所有特征可以任意组合，这些组合应被理解为本发明所公开的内容，除非本领域技术人员认为该组合明显不合理。本说明书所公开的数值点，不仅包括具体公开的数值点，还包括各数值范围的端点，这些数值点所任意组合的范围都应被视为本发明已公开或记载的范围，不论本文中是否一一公开了这些数值对。
(一)养殖微藻的方法
本发明提供了一种养殖微藻的方法，其中，在养殖微藻的培养基中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供，其中在养殖过程中，用硝酸和/或亚硝酸调节藻液的pH值。
根据本发明，养殖方式可以是光能自养(在光照下，仅利用无机碳源比如CO2生长)、异养培养(异养培养是指仅利用有机碳源生长)或光能兼养(光能兼养是指，在光照下同时利用无机碳源比如CO2和有机碳源生长)。
微藻生长需要必要的条件，比如，藻液需要适宜的温度，充足的光照(光能自养或光能兼养)，足够的水、CO2以及以营养液形式提供的氮肥、磷肥等营养物质，调控藻液中的溶解氧、pH值在合适的范围内等。尽管对于不同的微藻，这些条件不尽相同，但这些都是本领域已知的。
一般而言，培养温度为15～40℃，较佳的温度为25～35℃；藻液pH值为6～11，较佳的藻液pH值为7～9。光能自养或光能兼养时，光强为1000～200000勒克斯，较佳的光强为5000～150000勒克斯。
本发明人通过大量试验发现，对于光能自养或光能兼养的养殖方式，特别是当微藻代谢碱金属硝酸盐、碱金属亚硝酸盐、碱金属碳酸盐、碱金属碳酸氢盐、碱金属磷酸盐、碱金属磷酸氢盐之一或其任意组合时，如果在微藻的养殖过程中不向藻液中通入CO2或者不加入pH调节剂，则藻液的pH值会上升，特别当微藻代谢碱金属硝酸盐、碱金属亚硝酸盐或其组合时，藻液pH值呈现较快的上升趋势。一般养殖微藻的pH值为6～11，当培养基含有上述营养物质时，为了避免培养基的pH值超出微藻生长所允许的范围，本发明优选用硝酸和/或亚硝酸调节藻液的pH值。
本发明对微藻的种类没有限制。根据本发明，优选养殖那些适于产油的微藻，这样既可以获得生物能源，又可以减排废气污染物。
尽管异养培养或光能兼养会因使用有机碳源而增加部分养殖成本，但其养殖效率也大为提高，使后续加工过程得以简化，因此如果能够避免无菌养殖，就能够避免消耗大量蒸汽对系统进行严格灭菌处理，从而大幅降低养殖成本。根据本发明，特别优选那些能异养培养或光能兼养的微藻，比如小球藻、栅藻、螺旋藻或单针藻。令人惊讶的是，以异养培养或光能兼养方式培养这些微藻时，只要加入一定数量的EM菌，即使不进行消毒灭菌，养殖也会顺利进行，微藻的生长速率大大加快，即使水源含有大量有害细菌和/或敞开养殖，结果也是如此；而不加入EM菌时，异养培养或光能兼养通常会失败。
根据本发明，所述的异养培养或光能兼养中，优选不进行灭菌操作，也不加入杀菌剂，而是加入EM菌。
所述的EM菌(Effective Microorganisms)是本领域已知的，其主要由属于光合菌群、乳酸菌群、酵母菌群、革兰氏阳性放线菌群、发酵系的丝状菌群的几十种微生物组成，是一种市售的活菌制剂。所述的EM 菌既可根据现有技术自行配制，也可以通过商购获得，使用前需根据已有知识或商购制剂的说明进行发酵。
根据本发明，EM菌的用量应满足加速微藻生长的需要，既不能因用量过少而不起作用，又不能因用量过大而与微藻竞争消耗过多的营养物质。任何EM菌的加入方式(比如一次性加入或分多次加入)及任何的EM菌用量都是可用的，只要能满足加速微藻生长的需要。
根据本发明，EM菌的加入量为1×105个/L藻液～9×108个/L藻液，优选为1×106个/L藻液～5×108个/L藻液，进一步优选为1×106个/L藻液～1×108个/L藻液。
根据本发明，进行异养培养或光能兼养时，可用的有机碳源包括但不限于糖、有机酸、有机酸盐、醇、纤维素水解物和淀粉水解物中的至少一种；比如可选自葡萄糖、果糖、乙酸、乙酸钠、乳酸、乙醇、甲醇和纤维素水解物中的至少一种，较佳的选择是葡萄糖。
根据微藻生物量的增长情况以及培养基中营养物质的消耗情况，需要及时补充不足的营养物质。根据本发明，任何补加营养物质的方式都是可用的，比如分段补加或连续补加，只要能将营养物质的量控制在合适的范围内即可。
根据本发明，进行异养培养或光能兼养时，一般将有机碳源的浓度控制在1g/L藻液～30g/L藻液，优选控制在2g/L藻液～10g/L藻液。有机碳源可以一次性加入，也可以分多次加入。
根据本发明，所述碱金属营养盐中，金属离子为钠和/或钾。
根据本发明，所述的氮源优选为碱金属硝酸盐和/或碱金属亚硝酸盐。
根据本发明，所述的磷源优选为碱金属磷酸盐和/或碱金属磷酸氢盐。
根据本发明，所述碳源的一部分可以为碱金属碳酸盐和/或碱金属碳酸氢盐。
根据本发明，采用光能自养时，全部或大部分的碳源以CO2的形式提供。
根据本发明，所述的氮源、磷源、碳源的用量按现有已知的技术提供，比如以氮原子计，氮源的用量为0.1～400mmol/L，优选为10～300mmol/L，更进一步优选为20～200mmol/L。
根据本发明，还包括从收获的藻液中分离出微藻，并将分离出微藻后获得的养殖残液循环用于养殖微藻的步骤。
(二)养殖微藻与工业废气脱硝联合的方法
本发明提供了一种养殖微藻和工业废气脱硝的联合方法，包括以下步骤：
(1)养殖微藻的养殖步骤；
(2)将步骤(1)收获的藻液分离为湿微藻(藻泥)和养殖残液的分离步骤；
(3)用从步骤(2)获得的养殖残液完成对工业废气脱硝的NOx固定步骤；和
(4)任选地，将步骤(2)获得的藻泥干燥以得到微藻产品的干燥步骤；
其中，将从步骤(3)获得的固定了NOx的营养物流为步骤(1)的微藻养殖提供氮源。
上述步骤(3)可通过各种方式实施。
现有技术认为在微藻养殖中使用硝酸盐足以作为氮源，但一些情况下硝酸盐所含金属离子的累积可能会抑制藻生长。因此，在一个优选实施方案中，本发明所述联合方法涉及酸法工艺，其中所述步骤(3)包括：
(i)将工业废气中的NOx转化为硝酸和/或亚硝酸的步骤；和
(ii)将步骤(2)得到的养殖残液与步骤(i)中获得的硝酸和/或亚硝酸(优选硝酸和可选的亚硝酸)混合，从而实现对工业废气的脱硝。
在该实施方案中，用该混合得到的溶液作为所述固定了NOx的营养物流来为步骤(1)的微藻养殖过程提供氮源。
在另一个优选实施方案中，所述联合方法涉及碱法工艺，其中所述步骤(3)包括：
(i′)用步骤(2)得到的养殖残液直接固定工业废气中的NOx。在该实施方案中，用固定NOx后的营养物流为步骤(1)的养殖微藻过程提供氮源。
步骤(1)的实施可采用前述“养殖微藻的方法”中所述的任何具体实施方式，并可具有其中所述的特征、步骤、条件或其组合。
根据本发明，对待处理的工业废气中的NOx含量没有特别的限制。一般而言，工业废气中的NOx含量在几百ppm(体积)至几千ppm不等，比如在100ppm至5000ppm之间。
根据本发明，所述待处理的工业废气中，以NOx的总量计，NO所占的摩尔分数≥80％；进一步地，所述的工业废气中，以NOx的总量计，NO所占的摩尔分数≥90％。
根据本发明，在酸法工艺中，步骤(i)可采用任何已有的方法将工业废气中的NOx转化为硝酸和/或亚硝酸。
有些微藻不能够代谢NO2 -，当养殖这些微藻时，需要选择适当的固定NOx的方法，以使NOx大部分或全部转化为NO3 -。根据本发明，已知适当的方法都是可用的，比如以硝酸/双氧水为吸收剂的氧化吸收法。
根据本发明，优选养殖那些能同时代谢NO3 -和NO2 -的微藻，比如本发明筛选出的小球藻、单针藻、栅藻或螺旋藻，此时基本不存在转化NO2 -的问题。考虑到微藻养殖中的一些情况下氮源消耗较快，优选将该酸法工艺用于异养培养，和/或优选将该酸法工艺用于螺旋藻养殖。
根据本发明，在一个实施方式中，步骤(i)中，优选采用湿法脱硝将工业废气中的NOx转化为硝酸。湿法脱硝中用于吸收NOx的吸收液由0.5m％～58m％的硝酸、0.001m％～25m％的过氧化氢和余量水组成。这样的实施方式因而称为酸法工艺。
本发明人研究发现，对于酸法工艺，尽管采用高浓度硝酸/低浓度过氧化氢的水溶液或高浓度过氧化氢/低浓度硝酸的水溶液，都能够有效吸收低氧化度的NOx，然而这两种方法均存在过氧化氢分解较快、损耗较大的缺陷。在低浓度过氧化氢/低浓度硝酸的水溶液中，过氧化氢的分解较慢，然而低浓度过氧化氢/低浓度硝酸的水溶液对低氧化度NOx的吸收活性很低。本发明人经过深入研究意外发现，尽管在初始阶段，低浓度过氧化氢/低浓度硝酸的水溶液对低氧化度NOx的吸收活性很低，但随着时间的延长，该水溶液对低氧化度NOx的吸收活性缓慢升高，经过一段时间(活化阶段)后，该水溶液对低氧化度NOx的吸收活性进入高水平的稳定期。因此，优选，在一个实施方式中，本发明所述的低浓度过氧化氢/低浓度硝酸的吸收液在用于吸收NOx之前已经经历了所述活化阶段。
根据本发明，前述的湿法脱硝中，所述吸收液优选由10m％～25m％的硝酸、0.1m％～1m％的过氧化氢和余量水组成；更优选由10m％～25m％的硝酸、0.2m％～1m％的过氧化氢和余量水组成。如前所述，该组成的吸收液初始脱硝活性很低，必须经过一个活化阶段，才能满足对工业废气脱硝的要求。该活化阶段包括：将由10m％～25m％的硝酸、0.1m％～1m％ 的过氧化氢和余量水组成的溶液与含NOx的气体接触，当所述溶液的脱硝活性不再持续上升时，即完成活化步骤。所述含NOx的气体中，以NOx的总量计，NO所占的摩尔分数≥80％。所述用于活化吸收液的含NOx的气体可以为所述的工业废气。
根据本发明，前述的湿法脱硝中，脱硝温度可以为-10℃～40℃，脱硝压力可以为0.1Mpa～1Mpa；优选的脱硝温度和压力为常温和常压。
根据本发明，对前述湿法脱硝中工业废气与活性吸收液的接触方式没有特别的限制，比如可采用下述的(A)、(B)、(C)之一或其任意的组合：
(A)工业废气以气泡形态分散在吸收液中；
(B)吸收液以液滴状分散在工业废气中；
(C)液体以膜状运动与工业废气进行接触。
优选的情况下，采用上述的(A)方式。
根据本发明，所述的湿法脱硝中，可采用一个吸收塔或多个串联的吸收塔；优选采用一个吸收塔或2～3个串联的吸收塔。本发明对吸收塔的类型没有特别的限制，比如可采用下述之一或其任意的组合：板式吸收塔、鼓泡吸收塔、搅拌鼓泡吸收塔、将吸收液以液滴状分散在气相中的喷雾塔、填料吸收塔和降膜吸收塔；优选采用鼓泡吸收塔或搅拌鼓泡吸收塔。
在碱法工艺中，优选在步骤(1)中依靠微藻代谢调节培养基的pH值，使得从步骤(2)获得的养殖残液的pH值＞8，更优选使养殖残液的pH值为9～11。
如上所述，对于光能自养或光能兼养的养殖方式，特别是当微藻的培养基中含有碱金属硝酸盐、碱金属亚硝酸盐、碱金属碳酸盐、碱金属碳酸氢盐、碱金属磷酸盐、碱金属磷酸氢盐之一或其任意组合时，如果在微藻的养殖过程中，不提供或少提供CO2(或pH调节剂)，则藻液的pH值呈现上升的趋势。利用这一现象，可以在养殖微藻后期，不提供或少提供CO2(或pH调节剂)，依靠微藻代谢使养殖结束时的藻液呈碱性，这样就可以利用分离出微藻的养殖残液固定废气中的NOx或者中和固定NOx后的酸液，并随后用其为养殖微藻提供必需的氮源。因此，在一个实施方式中，通过调节养殖微藻步骤中CO2的供应量来使得养殖残液的pH值＞8，更优选为9～11。
发明人发现，利用分离出微藻后的碱性养殖残液可以高效率地固定废气中的NOx或者中和固定NOx后的酸液，得到含有NO3 -和/或NO2 - 的溶液，该溶液可以直接为下一批微藻养殖提供氮源，在该氮源被微藻代谢后，会再次使藻液呈碱性，通过这样一种模式可以在微藻养殖培养基与工业废气脱硝过程的吸收液或中和液之间实现封闭的循环，从而将“微藻养殖”与“工业废气脱硝”有机地联系起来，不仅可以利用微藻将氮污染物高效率地转化成有用的生物质，而且使“微藻养殖”与“废气脱硝”成为两个相对独立的过程，避免了二者的相互影响。
碱液吸收/固定法是一种成熟的废气脱硝工艺，关于利用碱性水溶液吸收/固定废气NOx的研究也很多，本发明可以采用这些已有方法中的任何一种。已知地，为了使NO固定完全，可在碱液吸收塔前增设氧化塔，利用废气中的余氧或添加臭氧将NO氧化为NO2，为碱液固定法提供最适宜的氧化度(NO2/NO摩尔比)。适于不同情况的催化氧化催化剂都是本领域已知的，比如用活性炭、活性碳纤维、高硅Na-ZSM-5分子筛或全硅β分子筛为催化剂在常温下将NO氧化成NO2。
根据本发明，步骤(i′)采用碱液吸收法吸收固定NOx，用于吸收固定废气NOx的吸收液采用微藻养殖过程中获得的养殖残液，并且不设置这些现有碱液固定工艺的提取硝盐步骤，而是将固定NOx后获得的溶液直接为养殖微藻提供氮源。
根据本发明，优选养殖那些能同时代谢NO3 -和NO2 -的微藻，比如本发明筛选出的小球藻、单针藻、栅藻或螺旋藻。
根据本发明，优选能够耐受高碱环境的微藻，养殖这些微藻可以进一步提高养殖残液的pH值，进而提高与硝酸和/或亚硝酸反应或者固定NOx的效率。发明人经过大量试验，筛选出以下能够耐高碱环境的微藻，比如小球藻、单针藻、栅藻或螺旋藻，这些微藻能够在pH为9～11的环境下健康生长。
根据本发明，优选那些在不通入CO2时能够依靠自身代谢迅速提高藻液pH值的微藻，养殖这些微藻可以进一步提高养殖微藻过程的效率。发明人经过大量试验，筛选出以下能够迅速提高藻液pH值的微藻，如小球藻、单针藻、栅藻或者螺旋藻，上述微藻能够在1～24小时内将藻液的pH值提高到9～11，使藻液满足高效与硝酸和/或亚硝酸反应或者吸收固定NOx的要求。
优选的情况下，从步骤(i′)得到的为微藻提供氮源的所述固定了NOx后的营养物流中，以氮原子计，含氮化合物的量为0.1～400mmol/L， 优选为10～300mmol/L，更进一步优选为20～200mmol/L。
工业废气中除了含有NOx外，可能还含有其他污染物比如SOx，本领域技术人员通过简单的试验(比如通过测定NOx固定率或者测定微藻生长速率的变化程度)，就能够确认废气中是否含有或者过量地含有对本发明的联合方法产生显著影响的污染物。发明人发现，当工业排放的烟气中的SOx含量较高时，会降低养殖残液对NOx的固定效率。根据需要，本领域技术人员也可以通过常规已知的技术手段，将废气中的SOx降低至不显著影响本发明的联合方法实施的水平。一般工业排放的烟气，尤其是燃煤烟气中含有大量SOx，因此对于这些工业废气，需要在本发明的废气脱硝前，将其含有的SOx去除。
根据本发明，所述的工业废气优选为不含有SOx或经过脱硫处理(脱除废气中的SOx)的工业废气。
应该理解到，本发明中的“微藻养殖”与“工业废气脱硝”是两个相对独立的过程，所述含CO2气体的主要功能是为微藻生长提供碳源，其基本不含有SOx和NOx。所述含CO2的气体可以为经过净化处理(脱除废气中的SOx和NOx)的工业废气，或者为不含有SOx和NOx的工业废气。
本发明构筑了一种减排工业废气污染物与生产微藻生物质的循环经济模式。利用工业排放的废气中的NOx来作为营养物流中的氮源，在减排污染物的同时，获得了有价值的微藻生物质。在这样一个循环经济的模式中，治理工业废气的部分成本用于培养微藻，工厂减少了废气、废水排放和对环境的污染，形成了封闭的循环，出口只有微藻生物质。
本发明的联合方法还可与附加的微藻养殖相结合，例如在初始阶段为该联合方法提供微藻，以及特别是当上述联合方法中的微藻需要补充时提供附加的微藻。该附加的微藻养殖可以是与该联合方法的微藻养殖步骤分开的独立过程，以在需要时向例如所述微藻养殖器输入微藻，例如参见图15。该附加的微藻养殖也可合并入所述联合方法中，例如处于上述微藻养殖步骤的下游。该附加的微藻养殖可以为光能自养、光能兼养和/或异养培养，使得产生的微藻量符合补充上述联合方法的需求。在一个实施方案中，该附加的微藻养殖为光能自养，采用本领域已知方法进行，例如参见图15所示的工艺流程。
在本发明中已经通过含NOx的工业废气与微藻养殖的联合方法进 行了例示说明，但本领域技术人员将能够理解的是，该联合方法也适用于任何其他需要脱硝的包含NOx的气体，只要该气体与微藻养殖相容。
(三)用于养殖微藻和工业废气脱硝的联合方法的系统(该部分待补充和完善)
本发明提供了用于养殖微藻和工业废气脱硝的联合方法的系统，其包含，任选从上游到下游地：
NOx固定单元，其具有含NOx工业废气入口、养殖残液入口、固定了NOx的营养物流出口和净化后的工业废气出口，以及任选地营养液入口，用于进行脱硝反应并提供固定了NOx的营养物流；
微藻养殖器，其具有固定了NOx的营养物流入口、藻种入口和藻液出口，以及任选地营养液入口任选地EM菌入口，用于利用所述固定了NOx的营养物流进行微藻养殖；
分离器，其具有藻液入口、藻泥出口和养殖残液出口，用于将从微藻养殖器收获的藻液分离为藻泥和养殖残液；和
循环线路，其连接分离器的养殖残液出口和NOx固定单元的养殖残液入口；
以及任选地，干燥器，用于干燥所述藻泥以得到微藻产品。
优选地，在酸法工艺中，所述NOx固定单元具有营养液入口。
优选地，在碱法工艺中，所述微藻养殖器具有营养液入口。
在一个优选实施方案中，所述联合方法涉及酸法工艺，其中所述NOx固定单元包含脱硝反应器和NOx固定营养物流配制器。
在一个优选实施方案中，所述联合方法涉及碱法工艺，其中所述NOx固定单元为脱硝反应器。
参见图13，本发明系统的一个实施方式包括：NOx固定单元1；微藻养殖器2；分离器3；和干燥器4。对于酸法工艺，所述NOx固定单元1包含：脱硝反应器1-1；和NOx固定营养物流配制器1-2(参见图14所示)；而对于碱法工艺，1为1-1：脱硝反应器。由此，在该系统中，将含NOx的气体A、来自分离器3以及任选地营养液E的养殖残液F送入NOx固定单元1中，处理后得到固定了NOx的营养物流B和净化后的气体C；随后，将来自NOx固定单元1的固定了NOx的营养物流B、藻种D以及任选地营养液E送入微藻养殖器2中；完成养殖的藻液送入分离器3，分 离得到湿微藻(藻泥)G和养殖残液F；将藻泥G送入干燥器4，进行干燥以得到微藻产品H。优选地，在酸法工艺中，将所述营养液E加入NOx固定单元1中。优选地，在碱法工艺中，将所述营养液E加入微藻养殖器2中。
图14例示了符合图13所示实施方式的酸法工艺。如上所述，在该酸法工艺中，所述NOx固定单元1由脱硝反应器1-1；和NOx固定营养物流配制器1-2构成。相应地，对于NOx固定单元1，将含NOx的气体A以及适当的作为NOx固定液的低浓度过氧化氢/低浓度硝酸的水溶液(图中未示出)送入脱硝反应器1-1中，处理后得到固定了NOx的营养物流和净化后的气体C；将所述固定了NOx的营养物流、来自分离器3以及营养液E的养殖残液F送入NOx固定单元1中，处理后得到固定了NOx的营养物流B。其余设施及工艺流程与图13所示的总的实施方式相同。
图15例示了本发明的联合方法与附加的微藻养殖相的组合。在该组合工艺中，本发明的联合方法具有如图13所示的工艺流程，区别在于，供应给微藻养殖器2的藻种D具体地来自一个附加的微藻养殖工艺，其为光能自养工艺。该附加的微藻养殖工艺在初始阶段为该联合方法提供微藻，以及特别是当上述联合方法中的微藻需要补充时提供附加的微藻。在图15所示的组合工艺中，该附加的微藻养殖可以是与该联合方法的微藻养殖步骤分开的独立过程，以在需要时向例如所述微藻养殖器输入微藻。
根据以上讨论，在一个方面，本发明提供了以下例示的实施方式：
1.一种养殖微藻的方法，其特征在于，养殖过程中，向藻液中加入EM菌。
2.根据实施方式1所述的方法，其特征在于，所述微藻是能异养培养或光能兼养的微藻。
3.根据实施方式2所述的方法，其特征在于，所述的微藻选自绿藻或蓝藻。
4.根据实施方式2所述的方法，其特征在于，所述的微藻是小球藻、栅藻、单针藻或螺旋藻。
5.根据实施方式2所述的方法，其特征在于，微藻养殖中所使用的有机碳源选自糖、有机酸、有机酸盐、醇、纤维素水解物和与淀粉水解物中的至少一种；优选葡萄糖、果糖、乙酸、乙酸钠、乳酸、乙醇、甲醇、纤维素水解物和纤维素水解物中的至少一种，更优选葡萄糖。
6.根据实施方式2或3所述的方法，其特征在于，将所用的有机碳源的浓度控制在1g/L藻液-30g/L藻液，优选控制在2g/L藻液-10g/L藻液。
7.根据实施方式1-6中任一项所述的方法，其特征在于，EM菌的加入量为1×105个/L藻液～9×108个/L藻液，优选为1×106个/L藻液～5×108个/L藻液，进一步优选为1×106个/L藻液～1×108个/L藻液。
8.根据实施方式1-7中任一项所述的方法，其特征在于，培养温度为15-40℃，藻液pH值为6-11。
9.根据实施方式1-8中任一项所述的方法，其特征在于，养殖方式为光能自养或光能兼养时，光强为1000-200000勒克斯。
10.根据实施方式1-9中任一项所述的方法，其特征在于，所述的养殖过程中，以NO3-和/或NO2-作为氮源，优选以工业废气脱硝所获得的硝盐和/或亚硝盐作为氮源。
11.根据实施方式1-10中任一项所述的方法，其中在养殖微藻的营养物流中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供；其特征在于，养殖过程中，用硝酸和/或亚硝酸调节藻液的pH值。
12.根据实施方式1-11中任一项所述的方法，其特征在于，所述硝酸通过采用湿法脱硝将工业废气中的NOx转化为硝酸而获得；湿法脱硝中的吸收液由0.5m％-58m％的硝酸，优选10m％-25m％的硝酸、0.001m％-25m％的过氧化氢，优选0.1m％-1m％的过氧化氢和余量水组成。
13.一种养殖微藻和工业废气脱硝的联合方法，包括以下步骤：
(1)养殖微藻的养殖步骤；
(2)将步骤(1)收获的藻液分离为湿微藻(藻泥)和养殖残液的分离步骤；
(3)用从步骤(2)获得的养殖残液完成对工业废气脱硝的NOx吸收固定步骤；和
(4)任选地，将步骤(2)获得的藻泥干燥以得到微藻产品的干燥步骤；
其中，将从步骤(3)获得的吸收了NOx的营养物流为步骤(1)的微藻养殖提供氮源。
14.根据实施方式13所述的联合方法，其特征在于，所述步骤(1)的养殖微藻的养殖步骤采用实施方式1-12中任一项所述的方法进行。
15.根据实施方式13或14所述的联合方法，其特征在于，所述联合方法为酸法工艺，其中所述步骤(3)包括：
(i)将工业废气中的NOx转化为硝酸和/或亚硝酸的步骤；和
(ii)将步骤(2)得到的养殖残液与步骤(i)中获得的硝酸和/或亚硝酸混合，从而实现对工业废气的脱硝。
16.根据实施方式13或14所述的联合方法，其特征在于，所述联合方法为碱法工艺，其中所述步骤(3)包括：
(i′)用步骤(2)得到的养殖残液直接吸收工业废气中的NOx。
17.根据实施方式13-16中任一项所述的方法，其特征在于，当养殖方式为光能自养或光能兼养时，用含CO2的气体作为无机碳源，优选所述含CO2的气体为经过净化处理的工业废气，或者为不含有SOx和NOx的工业废气。
18.根据实施方式13-17中任一项所述的方法，其特征在于，在所述吸收了NOx的营养物流中，以氮原子计，含氮化合物的量为0.1-400mmol/L，优选为10-300mmol/L，更进一步优选为20-200mmol/L。
19.根据实施方式13-18中任一项所述的方法，其特征在于，所述的工业废气为不含有SOx的工业废气或经过脱硫处理的工业废气。
20.根据实施方式13-19中任一项所述的方法，其特征在于，
在养殖微藻后期，不提供或少提供CO2或pH调节剂，依靠微藻代谢碱金属营养盐使养殖结束时的藻液呈养殖；所述的碱金属营养盐为碱金属硝酸盐、碱金属亚硝酸盐、碱金属碳酸盐、碱金属碳酸氢盐、碱金属磷酸盐、碱金属磷酸氢盐之一或它们的组合，优选碱金属硝酸盐和/或碱金属亚硝酸盐。
在另一个方面，本发明提供了以下例示的实施方式：
1.一种养殖微藻的方法，养殖微藻的营养物流中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供；其特征在于，养殖过程中， 用硝酸和/或亚硝酸调节藻液的pH值。
2.根据实施方式1所述的方法，其特征在于，养殖过程中，向藻液中加入EM菌。
3.根据实施方式2所述的方法，其特征在于，EM菌的加入量为1×105个/L藻液～9×108个/L藻液，优选为1×106个/L藻液～5×108个/L藻液，进一步优选为1×106个/L藻液～1×108个/L藻液。
4.根据实施方式1-3中任一项所述的方法，其特征在于，所述微藻是能异养培养或光能兼养的微藻。
5.根据实施方式1-4中任一项所述的方法，其特征在于，所述的微藻为绿藻或蓝藻，优选小球藻、栅藻、单针藻或螺旋藻。
6.根据实施方式1-5中任一项所述的方法，其特征在于，所述硝酸通过采用湿法脱硝将工业废气中的NOx转化为硝酸而获得；湿法脱硝中的吸收液由0.5m％～58m％的硝酸，优选10m％～25m％的硝酸、0.001m％～25m％的过氧化氢，优选0.1m％～1m％的过氧化氢和余量水组成。
7.按照实施方式4所述的方法，其特征在于，所使用的有机碳源选自糖、有机酸、有机酸盐、醇、纤维素水解物和与淀粉水解物中的至少一种。
8.按照实施方式4所述的方法，其特征在于，所使用的有机碳源的浓度控制在1g/L藻液～30g/L藻液。
9.按照实施方式1所述的方法，其特征在于，当养殖方式为光能自养或光能兼养时，光强为1000～200000勒克斯。
10.一种养殖微藻和工业废气脱硝的联合方法，包括以下步骤：
(1)养殖微藻的养殖步骤；
(2)将步骤(1)收获的藻液分离为湿微藻(藻泥)和养殖残液的分离步骤；
(3)用从步骤(2)获得的养殖残液完成对工业废气脱硝的NOx吸收固定步骤，其包括：
(i)将工业废气中的NOx转化为硝酸和/或亚硝酸的步骤；和
(ii)将步骤(2)得到的养殖残液与步骤(i)中获得的硝酸和/或亚硝酸混合固定了NOx的营养物流，从而实现对工业废气的脱硝；和
(4)任选地，将步骤(2)获得的藻泥干燥以得到微藻产品的干燥 步骤；
其中，将从步骤(3)获得的固定了NOx的营养物流为步骤(1)的微藻养殖提供氮源。
11.根据实施方式10所述的方法，其特征在于，步骤(2)中，采用湿法脱硝将工业废气中的NOx转化为硝酸；湿法脱硝中的吸收液由0.5m％～58m％，优选10m％～25m％的硝酸、0.001m％～25m％，优选0.1m％～1m％的过氧化氢和余量水组成。
12.根据实施方式10或11所述的联合方法，其特征在于，所述步骤(1)的养殖微藻的养殖步骤采用实施方式1-9中任一项所述的方法进行。
13.按照实施方式10-12中任一项所述的联合方法，其特征在于，所述步骤(1)的营养物流中，氮源以碱金属硝酸盐和/或碱金属亚硝酸盐的形式提供。
14.根据实施方式10-13中任一项所述的联合方法，其特征在于，该联合方法还包含附加的微藻养殖步骤，其在初始阶段为该联合方法提供微藻，和/或在所述微藻养殖步骤(1)中的微藻需要补充时提供附加的微藻。
15.根据实施方式14所述的联合方法，其特征在于，该附加的微藻养殖步骤是与所述藻养殖步骤(1)分开的独立过程，以在需要时向所述藻养殖步骤(1)输入微藻。
16.根据实施方式14所述的联合方法，其特征在于，该附加的微藻养殖步骤合并入所述联合方法中，并处于所述藻养殖步骤(1)的上游。
17.用于养殖微藻和工业废气脱硝的联合方法的系统，其包含，任选从上游到下游地：
NOx固定单元，用于对工业废气进行脱硝反应并提供吸收固定了NOx的营养物流；
微藻养殖器，用于利用所述固定了NOx的营养物流进行微藻养殖；
分离器，用于将从微藻养殖器收获的藻液分离为藻泥和养殖残液；和
循环线路，用于将来自所述分离器的养殖残液循环回工艺上游，用于固定工业废气中的NOx；
以及任选地，干燥器，用于干燥所述藻泥以得到微藻产品。
18.实施方式17所述的系统，其中所述NOx吸收单元具有含NOx的工业废气入口、养殖残液入口、固定了NOx的营养物流出口和净化后的工业废气出口；
所述微藻养殖器具有固定了NOx的营养物流入口、藻种入口和藻液出口；
所述分离器具有藻液入口、藻泥出口和养殖残液出口；和
所述循环线路连接分离器的养殖残液出口和NOx吸收单元的养殖残液入口。
19.实施方式18所述的系统，其中所述NOx吸收单元包含脱硝反应器和NOx固定营养物流配制器。
20.根据实施方式18或19所述的系统，其特征在于，该系统还包含附加的微藻养殖设备，其在初始阶段为该系统提供微藻，和/或在所述微藻养殖器中的微藻需要补充时提供附加的微藻。
实施例
下面通过实施例详细说明本发明。
藻液光密度值(OD680值)测定：光密度值用分光光度计测定，以蒸馏水作对照，测定藻液在波长680nm处的吸光值，作为微藻浓度的指标。
溶液氮含量的测定：采用ICS3000型离子色谱仪(美国Dionex公司)测定水溶液中的NO3 -含量或者NO2 -含量，仪器配有EG40淋洗液自动发生器、电导检测器和变色龙色谱工作站；IonPac AS11-HC型分离柱(250mm×4mm i.d.)；IonPac AG11型保护柱(50mm×4mm i.d.)；ASRS-ULTRA阴离子自身抑制器。淋洗液：KOH溶液；流速为1mL/min；淋洗液浓度：30mmol/L；进样量为60μL；柱温为30℃；抑制电流100mA；外标法峰面积定量。
细菌计数：按以下步骤进行细菌计数
1.样品洗涤：吸取1ml样品，用1×PBS洗涤2-3次；2.初步分离：根据藻类和细菌离心力的不同，首先用1000rpm离心2min，初步分离藻类(细菌在上清液中，藻类呈沉淀)；如果藻类含量较高时，再次重复；3.收集上清，此时上清中的藻类数量可忽略不计，8000rpm离心5min， 弃上清；4.用500ul细菌破膜剂重悬沉淀，室温反应15min；5.8000rpm离心5min，用1×PBS洗涤2次菌液；6.加入100ul 1×PBS重悬菌体，加入5ul PI染液母液，室温反应30min；7.荧光显微镜下观察细菌并计数，4个大方格内细菌数量最高为1000个，大于1000个时，稀释菌液一定倍数重新计数；8.计算公式：
所测溶液中细菌密度＝计数结果/4×稀释倍数×4×104个/ml
主要试剂耗材：
Figure PCTCN2015000181-appb-000001
主要仪器：
所用仪器 生产厂家
计数板 上海精密仪器
荧光显微镜 Olympus BX-51
微藻的培养基：培养基成分见表1～表5。
本发明中，所述的脱硝活性是指处理后工业废气的NOx含量占处理前工业废气的NOx含量的摩尔分数。
表1 培养基BG11
Figure PCTCN2015000181-appb-000002
表2 微量元素A5
Figure PCTCN2015000181-appb-000003
表3 Z氏培养基
Figure PCTCN2015000181-appb-000004
表4 异养培养基
Figure PCTCN2015000181-appb-000005
表5 微量元素
Figure PCTCN2015000181-appb-000006
实施例1
本实施例用于说明“添加EM菌对微藻光能自养的影响”。
采用BG11培养基(按表1添加营养成分，培养基不进行灭菌处理)培养小球藻，控制温度为20～30℃之间，通入压缩空气与CO2培养，当藻液PH＞10时通入CO2，当藻液PH＜7.5时停止通入CO2。培养过程中采用自然日光培养，控制白天光照强度最高可达60000勒克斯，每天检测藻液的OD680值，连续培养14天后收获，培养结束前1天停止通入含CO2的混合气，结束养殖后，通过离心分离得到藻泥与养殖残液。微藻的生长曲线见图1，图1中的两个试验基本相同，区别仅在于：其中一个试验不添加EM菌，另一个试验按3.6×106个/L藻液的添加量添加EM菌。对于添加EM菌的试验，养殖过程中监测藻液的细菌计数＜6.7×106个/mL藻液，测得养殖结束时藻液pH自然升高到9.8。从图1中可见，在光能自养条件下，添加EM菌促进了微藻的生长。
实施例2～5用于说明“光能兼养中，EM菌添加量对微藻培养的影响”。
实施例2
采用BG11培养基(按表1添加营养成分，培养基不进行灭菌处理)培养小球藻，培养过程加入2g/L的葡萄糖，控制温度为20～30℃之间，通入压缩空气与CO2培养，当藻液PH＞10时通入CO2，当藻液PH＜7.5时停止通入CO2。培养过程中采用自然日光培养，控制白天光照强度最高可达60000勒克斯，每天检测藻液的OD680值，微藻的生长曲线见图2。其中EM添加量为3.6×106个/L藻液，养殖过程中监测藻液的细菌计 数＜8×106个/mL藻液，连续培养14天后收获，培养结束前1天停止通入CO2烟气，并使藻液pH自然升高到9.4，然后结束养殖，离心分离得到藻泥与养殖残液。
实施例3
本实施例与实施例2基本相同，区别仅在于：EM添加量为1.8×107个/L藻液。添加EM后，在养殖过程中待体系达到稳态后监测藻液的细菌计数＜1×107个/mL藻液，测得培养结束时藻液的pH自然升高到9.3。微藻的生长曲线见图2。
实施例4
本实施例与实施例2基本相同，区别仅在于：EM添加量为3.6×107个/L藻液。添加EM后，在养殖过程中待体系达到稳态后监测藻液的细菌计数＜2×107个/mL藻液，测得培养结束时藻液的pH自然升高到8.9。微藻的生长曲线见图2。
实施例5
本实施例与实施例2基本相同，区别仅在于：EM添加量为7.2×107个/L藻液。养殖过程中监测藻液的细菌计数＜5.8×107个/mL藻液，测得培养结束时藻液的pH自然升高到8.7。微藻的生长曲线见图2。
对比例1
本对比例与实施例2基本相同，区别仅在于：不添加EM菌。养殖过程中监测藻液的细菌计数最高达到了1.2×108个/mL藻液，测得培养结束时藻液的pH自然升高到7.9。微藻的生长曲线见图2。
从图2中可见，在光能兼养条件下，添加EM菌促进了微藻的生长。
实施例6～8用于说明“微藻对硝酸盐和亚硝酸盐的代谢”。
实施例6
采用BG11培养基(按表1添加营养成分，培养基不进行灭菌处理)培养小球藻，控制温度为20～30℃之间，通入压缩空气与CO2培养，当藻液PH＞10时通入CO2，当藻液PH＜7.5时停止通入CO2。培养过程中采用自然日光培养，控制白天光照强度最高可达60000勒克斯，每天检测藻液的OD680值，连续培养14天。微藻的生长曲线见图3。
实施例7
本实施例与实施例6基本相同，区别仅在于：将培养基中1.5g/L的硝酸钠替换成1.35g/L亚硝酸钠以及0.15g/L硝酸钠。微藻的生长曲线见 图3。
实施例8
本实施例与实施例7基本相同，区别仅在于：培养微藻为单针藻。微藻的生长曲线见图3。
从图3可见，采用所选育的微藻藻种，可以同时利用硝酸盐和亚硝酸盐较好地生长。
实施例9～16用于说明“在大量添加有机碳源的情况下，EM菌对微藻代谢无机氮源的影响”。
实施例9
首先采用BG11培养基(按表1添加营养成分，培养基不进行灭菌处理)培养小球藻；当OD680值为4时，按表4规定量补加一次异养培养基营养成分。控制温度为20～30℃之间，通入压缩空气与CO2培养，当藻液PH＞10时通入CO2，当藻液PH＜7.5时停止通入CO2。培养过程中采用自然日光培养，控制白天光照强度最高可达60000勒克斯，添加2g/L的葡萄糖，并按2.9×107个/L藻液的量添加EM菌，每天检测藻液的OD680值；培养1天后再次加入10g/L的葡萄糖，并按3.6×107个/L藻液补加EM菌；培养至第5天时再次补加葡萄糖10g/L，养殖过程中监测藻液的细菌计数最高为9.7×106个/mL藻液，连续培养8天后收获，最后一次加入葡萄糖后停止通入CO2，结束养殖时藻液PH值为8.6，离心分离得到藻泥与养殖残液。分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻的生长曲线见图4。
实施例10
本实施例与实施例9基本相同，区别仅在于：培养微藻为单针藻。养殖过程中监测藻液的细菌计数最高达到了4.6×107个/mL藻液，测得培养结束时藻液的pH自然升高到8.2，分析养殖残液中的NO3 -与NO2 -的总含量＜200μg/g。微藻的生长曲线见图4。
实施例11
本实施例与实施例9基本相同，区别仅在于以下方面：第一次的EM菌添加量为7.9×107个/L藻液，不添加第二次的EM菌；并且第二次添加的葡萄糖量为30g/L，不添加第三次葡萄糖。养殖过程中监测藻液的细菌计数最高为2.6×107个/mL藻液，测得培养结束时藻液的pH自然升高到8.2，分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻 的生长曲线见图4。
实施例12
本实施例与实施例11基本相同，区别仅在于：培养微藻为单针藻。养殖过程中监测藻液的细菌计数最高达到了5.2×107个/mL藻液，测得培养结束时藻液的pH自然升高到7.8，分析养殖残液中的NO3 -与NO2 -的总含量＜200μg/g。微藻的生长曲线见图4。
对比例2
本对比例与实施例9基本相同，区别仅在于：不添加EM菌。监测培养过程中藻液细菌计数最高为13.6×108个/mL藻液，测得培养结束时藻液的pH自然升高到7.2。微藻的生长曲线见图4。
从图4中可见，添加EM菌大大促进了微藻的生长并迅速消耗了无机氮源。
实施例13
首先采用BG11培养基(按表1添加营养成分，培养基不进行灭菌处理)培养小球藻；当OD680值为4时，按表4规定量补加一次异养培养基营养成分。控制温度为20～30℃之间，通入压缩空气与CO2培养，当藻液PH＞10时通入CO2，当藻液PH＜7.5时停止通入CO2。培养过程中采用自然日光培养，控制白天光照强度最高可达60000勒克斯，小球藻接种后首先在光照自养条件下培养2天，然后添加2g/L的葡萄糖，并按1.8×108个/L藻液的量添加EM菌，每天检测藻液的OD680值；培养3天后再次加入10g/L的葡萄糖，并按1.8×108个/L藻液补加EM菌；培养2天后再次补加葡萄糖10g/L，养殖过程中监测藻液的细菌计数最高为2.9×107个/mL藻液，连续培养14天后收获，最后一次加入葡萄糖后停止通入CO2，结束养殖时藻液PH值为9.2，离心分离得到藻泥与养殖残液。分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻的生长曲线见图5。
实施例14
本实施例与实施例13基本相同，区别仅在于以下方面：不添加第二次的EM菌；并且第二次添加的葡萄糖量为30g/L，不添加第三次葡萄糖。养殖过程中监测藻液的细菌计数最高为2.9×107个/mL藻液，测得培养结束时藻液的pH自然升高到9.3，分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻的生长曲线见图5。
实施例15
本实施例与实施例13基本相同，区别仅在于：BG11培养基中NaNO3替换为KNO3，并且KNO3添加量为0.5g/L。养殖过程中监测藻液的细菌计数最高为1.3×107个/mL藻液，测得结束养殖时藻液的PH值为9.4，分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻的生长曲线见图5。
实施例16
本实施例与实施例14基本相同，区别仅在于：BG11培养基中的NaNO3替换为KNO3，并且KNO3添加量为0.5g/L。养殖过程中监测藻液的细菌计数最高为1.7×107个/mL藻液，测得结束养殖时藻液的PH值为9.3，分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g。微藻的生长曲线见图5。
从图5中可见，以硝酸钾或硝酸钠作为氮源，添加EM菌均促进了微藻的生长。
实施例17～18用于说明“利用养藻获得的养殖残液固定NOx并用固定NOx后的溶液继续养殖微藻的情况”。
实施例17
采用O3辅助法吸收NOx。
采用NO2与NO的混合气模拟实际烟气，以压缩空气为载气，NOx流量为0.3L/min，含O3的气体来自青岛欣美净化设备有限公司生产的XM-Y型移动臭氧发生器，流量为1L/min，混合空气后使总流量达150L/h，测量入口与出口气体的NOx浓度，以下式计算NOx固定率；
NOx固定率＝(1-出口NOx浓度/入口NOx浓度)×100％；
其中入口NOx的总浓度基本稳定在620mg/m3(其中NO含量约为600mg/m3，NO2含量约为20mg/m3)
流程图见图6，其中吸收塔直径100mm，高700mm，塔底部装有筛孔状气体分布器，其中盛放3L实施例16产生的养殖残液。操作时将NOx混合气体直接通入吸收塔，吸收22h停止操作，将碱塔内的养殖残液取出，测定其中的NO3 -与NO2 -的总含量为5900μg/g。
利用NOx固定液养殖微藻。
将上述NOx固定液作为微藻培养基，除氮源外的其他营养物质按BG11培养基提供，养殖小球藻，养殖方法的其余部分同实施例16，养殖过程中监测藻液的细菌计数最高为1.8×107个/mL藻液，连续培养14天后收获，最后一次加入葡萄糖后停止通入CO2，结束养殖时藻液PH值为9.1，离心分离得到藻泥与养殖残液。分析养殖残液中的NO3 -与NO2 -的总含量＜10μg/g，从图7中可见，采用固定了NOx的营养物流为养殖营养液，添加EM菌后可促进了微藻的生长，再一次将藻液中的NO3 -和NO2 -固定，并恢复到碱性，从而可以进一步作为废气脱硝的碱性固定液。
实施例18
按实施例17的方法固定NOx，不同之处仅在于：吸收塔中盛放实施例10得到的3L养殖残液。固定22h后，将碱塔内的养殖残液取出，测定其中的NO3 -与NO2 -的总含量为5800μg/g。
利用NOx固定液养殖微藻。
将上述NOx固定液作为微藻培养基，除氮源外的其他营养物质按BG11培养基提供，养殖单针藻，养殖方法的其余部分同实施例10，养殖过程中监测藻液的细菌计数最高为9.2×106个/mL藻液，连续培养8天后收获，最后一次加入葡萄糖后停止通入CO2烟气，结束养殖时藻液PH值为8.7，离心分离得到藻泥与养殖残液。分析养殖残液中的NO3 -与NO2 -的总含量＜200μg/g，从图8中可见，采用NOx固定液为养殖营养液，添加EM菌后可促进了微藻的生长，再一次将藻液中的NO3 -和NO2 -固定，并恢复到碱性，从而可以进一步作为脱硝的碱性固定液。
实施例19用于说明“EM菌对微藻无光异养的影响”。
实施例19
本实施例与实施例9基本相同，区别仅在于：在无光条件下培养。测得结束养殖时藻液的pH值为7.7。微藻的生长曲线见图9。
对比例3
本对比例用于说明“EM菌对NOx的固定同化情况”。
本对比例与实施例9基本相同，区别仅在于以下方面：单纯培养 EM菌；培养前对培养基进行灭菌处理；培养基仍采用BG11(表1)，但NO3 -的初始浓度为6900ug/g；培养14天。分析培养结束时的NO3 -和NO2 -总含量为5600ug/g。可见，EM菌在生长过程中对无机氮源的消耗速率远低于微藻。
实施例20
本实施例用于说明用碱性养殖残液固定NOx。
取实施例14的碱性养殖残液3L；分析该碱性养殖残液中的钾、钠离子浓度，配制与其具有相同钾离子浓度和钠离子浓度的水溶液3L，配对阴离子为HCO3 -和CO3 2-，所配制的水溶液pH值为9.27，与实施例14的碱性养殖残液的pH值基本相同。分别以上述的碱性养殖残液和配制的水溶液为固定液，采用实施例17的方法固定NOx，对NOx的固定效率曲线见图10。
由图10可见，养殖残液对NOx的固定率明显高于配制的碱液。
对比例4
本对比例用于说明用低浓度NH4HCO3培养小球藻的效果。
采用BG11培养基(表1)培养小球藻，将BG11培养基中的氮源改为NH4HCO3，氮源浓度为3.3mmol/L，该氮源浓度远低于BG11培养基中的氮源浓度(17.6mmol/L)。藻种起始浓度OD680为0.5，通入压缩空气培养，控制温度为20～30℃之间。培养过程中采用自然日光培养，控制白天光照强度最高可达60000lux。其生长曲线见图1。
对比例5
本对比例用于说明用低浓度NaNO3培养小球藻的效果。
与对比例4基本相同，不同之处仅在于：将培养基中的氮源改为NaNO3。每天检测藻液的OD680值，其生长曲线见图1。
对比例6
本对比例用于说明用极高浓度NaNO3培养小球藻的效果。
与对比例4基本相同，不同之处仅在于：将培养基中的氮源改为NaNO3，氮源浓度增加至176mmol/L，该氮源浓度远高于BG11培养基中的氮源浓度(17.6mmol/L)。每天检测藻液的OD680值，其生长曲线见图1。
实施例20
本实施例用于说明本发明在自养培养小球藻时的效果。
本实施例与对比例4基本相同，不同之处仅在于：氮源及其浓度仍采用BG11培养基的配方，培养后期当pH值高于10时，补充硝酸将pH调整在合适的范围内，每天检测藻液的OD680值，其生长曲线见图1。
实施例21
本实施例用于说明本发明在自养培养螺旋藻时的效果。
采用Z氏培养基(表3)养殖螺旋藻，藻种起始浓度OD680为0.3，通入压缩空气培养，控制温度为20～30℃之间，当pH值高于10.5时，补充硝酸将pH调整在合适的范围内。培养过程中采用自然日光培养，控制白天光照强度最高可达60000lux。每天检测藻液的OD680值，其生长曲线见图2。
实施例22
本实施例用于说明本发明在兼养培养小球藻时的效果(不进行灭菌操作)。
本实施例与同对比例4基本相同，不同之处仅在于：采用小球藻异养培养基(表4)，培养过程中每三天添加葡萄糖2g/L和EM菌5×107个/L藻液，当pH值高于10时，补充硝酸将pH调整在合适的范围内。每天检测藻液的OD680值，其生长曲线见图1。
实施例23
本实施例用于说明本发明在兼养培养螺旋藻时的效果(不进行灭菌操作)。
本实施例与实施例21基本相同，不同之处仅在于：培养过程中，每三天添加葡萄糖2g/L和EM菌5×107个/L藻液，当pH值高于10.5时，补充硝酸将pH调整在合适的范围内。每天检测藻液的OD680值，其生长曲线见图2。
实施例24
本实施例用于说明本发明在无菌异养培养小球藻时的效果。
小球藻与对比例4基本相同，采用小球藻异养培养基(表4)进行异养 培养，藻种起始浓度OD680为0.5，通入压缩空气，在无菌、无光状态下培养，控制温度为20～30℃之间。当葡萄糖消耗殆尽时及时添加葡萄糖10g/L；当pH值高于10时，补充硝酸将pH调整在合适的范围内。每天检测藻液的OD680值，其生长曲线见图1。
由图11～12可见，采用本发明的方法，能提高微藻的生长效率。如果在养殖初期大量添加硝酸盐，则高浓度硝酸盐并不会显著促进微藻的生长。
实施例25
本实施例用于说明硝酸或H2O2浓度变化对过氧化氢分解速率的影响。
配制不同浓度的硝酸/H2O2水溶液，10天后测定H2O2的浓度，计算不同浓度的硝酸/H2O2水溶液中的H2O2分解率，结果见表6。(用GB1616-2003的方法测定过氧化氢浓度)
表6
Figure PCTCN2015000181-appb-000007
表6可见，不论提高硝酸浓度，还是提高过氧化氢浓度，都导致过氧化氢的损耗显著增加。
实施例26
本实施例用于说明本发明对低浓度NOx的脱硝效果。
模拟废气用NO、NO2和氮气配制，NO的浓度为500ppm(体积)，NO2的浓度为20ppm(体积)。吸收液由15m％的硝酸、0.4m％的过氧化氢和余量水组成。吸收装置采用玻璃塔，玻璃塔直径为100mm，高为700mm；在玻璃塔的底部设有筛板，筛板孔径为16μm～30μm；塔内装有3000ml吸收液；模拟废气的流速为150L/h；试验在常温、常压下进行。试验结果见表7。(用GB/T14642-2009的方法测定，发现试验后的吸收液中无亚硝 酸根)
表7
处理时间/h 1 2 4 8 12 16 20 26 31 36 41 47
出口NO/ppm 460 420 360 260 150 35 30 24 20 17 21 19
出口NO2/ppm 1 0 0 0 0 5 10 13 18 23 19 21
出口NOx/ppm 461 420 360 260 150 40 40 37 38 40 40 40
表7可见，在脱硝初始阶段，吸收液的脱硝活性很低，随时间增加，吸收液脱硝活性缓慢持续增加，16小时后吸收液的脱硝活性进入稳定期，此时的脱硝率达到90％以上。
实施例27
本实施例用于说明本发明对低浓度NOx的脱硝效果。
本实施例与实施例26基本相同，不同之处仅在于：过氧化氢的浓度为1m％，硝酸的浓度为25m％。试验结果见表8。(用GB/T14642-2009的方法测定，发现试验后的吸收液中无亚硝酸根)
表8
时间/h 1 2 4 8 12 16 20
出口NO/ppm 430 400 330 220 100 36 27
出口NO2/ppm 0 0 0 0 0 2 11
出口NOx/ppm 430 400 330 220 100 38 38
实施例28
本实施例用于说明，本发明采用单塔时对高浓度NOx的脱硝效果。
本实施例与实施例26基本相同，不同之处仅在于：过氧化氢的浓度为0.3m％，硝酸的浓度为15m％；模拟废气中，NO的浓度为3200ppm(体积)，NO2的浓度为100ppm(体积)。试验结果见表9。(用GB/T14642-2009的方法测定，发现试验后的吸收液中无亚硝酸根)
表9
时间/h 1 2 4 8 12 16 20 24 30 35 40 45
出口NO/ppm 2310 1900 1600 1400 1300 1250 1200 1000 830 750 800 830
出口NO2/ppm 60 50 35 35 30 30 50 120 290 320 290 260
出口NOx/ppm 2370 1950 1635 1435 1330 1280 1250 1120 1110 1070 1090 1090
对比例7
本对比例用于说明采用高浓度H2O2时的脱硝效果。
本实施例与实施例26基本相同，不同之处仅在于：过氧化氢的浓度为2.5m％，硝酸的浓度为15m％。试验结果见表10。
表10
时间/h 1 2 4 8 12 16 20
NO/ppm 59 20 50 30 25 25 35
NO2/ppm 14 25 15 20 20 15 10
NOx/ppm 73 45 75 50 45 40 35
实施例29
本实施例用于说明采用本发明所述系统时的酸法工艺流程。
参见图14，150L/h含480ppm NO其余为空气的混合气体首先进入脱硝反应器1-1(含有0.5％的双氧水和15％稀硝酸的水溶液)中进行反应，得到稀硝酸，硝酸的产率为0.19kg/h，经过固定后的净化气体C放空。
将微藻营养液E 3kg送入NOx固定营养物流配制器1-2中(营养液成分为Z氏培养基+10g/L NaNO3)，与养殖残液F、稀硝酸混合均匀后送入微藻养殖器2中，在微藻养殖器2中加入一定浓度的藻种D使最终藻液浓度为OD＝0.3，并向微藻养殖器2中通入浓度2％(体积浓度)的CO2，CO2的流量是200L/h，当藻液pH＜8.5时停止通入CO2，当藻液pH＞10.5时继续通入CO2，光照强度为10000勒克斯。
完成养殖后，藻液送入微藻过滤分离器3中进行过滤分离，得到的养殖残液F2.5kg返回NOx固定营养物流配制器1-2中进行循环培养。经过浓缩的藻泥G 250g送入微藻干燥器4中进行干燥，得到25g的微藻产品。

Claims (20)

  1. 一种养殖微藻的方法，养殖微藻的营养物流中，氮源、磷源和碳源中的至少一种以碱金属营养盐的形式提供；其特征在于，养殖过程中，用硝酸和/或亚硝酸调节藻液的pH值。
  2. 根据权利要求1所述的方法，其特征在于，养殖过程中，向藻液中加入EM菌。
  3. 根据权利要求2所述的方法，其特征在于，EM菌的加入量为1×105个/L藻液～9×108个/L藻液，优选为1×106个/L藻液～5×108个/L藻液，进一步优选为1×106个/L藻液～1×108个/L藻液。
  4. 根据权利要求1-3中任一项所述的方法，其特征在于，所述微藻是能异养培养或光能兼养的微藻。
  5. 根据权利要求1-4中任一项所述的方法，其特征在于，所述的微藻为绿藻或蓝藻，优选小球藻、栅藻、单针藻或螺旋藻。
  6. 根据权利要求1-5中任一项所述的方法，其特征在于，所述硝酸通过采用湿法脱硝将工业废气中的NOx转化为硝酸而获得；湿法脱硝中的吸收液由0.5m％～58m％的硝酸，优选10m％～25m％的硝酸、0.001m％～25m％的过氧化氢，优选0.1m％～1m％的过氧化氢和余量水组成。
  7. 按照权利要求4所述的方法，其特征在于，所使用的有机碳源选自糖、有机酸、有机酸盐、醇、纤维素水解物和淀粉水解物中的至少一种。
  8. 按照权利要求4所述的方法，其特征在于，所使用的有机碳源的浓度控制在1g/L藻液～30g/L藻液。
  9. 按照权利要求1所述的方法，其特征在于，当养殖方式为光能自养或光能兼养时，光强为1000～200000勒克斯。
  10. 一种养殖微藻和工业废气脱硝的联合方法，包括以下步骤：
    (1)养殖微藻的养殖步骤；
    (2)将步骤(1)收获的藻液分离为湿微藻(藻泥)和养殖残液的分离步骤；
    (3)用从步骤(2)获得的养殖残液完成对工业废气脱硝的NOx固定步骤，其包括：
    (i)将工业废气中的NOx转化为硝酸和/或亚硝酸的步骤；和
    (ii)将步骤(2)得到的养殖残液与步骤(i)中获得的硝酸和/或亚硝酸混合固定了NOx的营养物流，从而实现对工业废气的脱硝；和
    (4)任选地，将步骤(2)获得的藻泥干燥以得到微藻产品的干燥步骤；
    其中，将从步骤(3)获得的固定了NOx的营养物流为步骤(1)的微藻养殖提供氮源。
  11. 根据权利要求10所述的方法，其特征在于，步骤(2)中，采用湿法脱硝将工业废气中的NOx转化为硝酸；湿法脱硝中的吸收液由0.5m％～58m％，优选10m％～25m％的硝酸、0.001m％～25m％，优选0.1m％～1m％的过氧化氢和余量水组成。
  12. 根据权利要求10或11所述的联合方法，其特征在于，所述步骤(1)的养殖微藻的养殖步骤采用权利要求1-9中任一项所述的方法进行。
  13. 按照权利要求10-12中任一项所述的联合方法，其特征在于，所述步骤(1)的营养物流中，氮源以碱金属硝酸盐和/或碱金属亚硝酸盐的形式提供。
  14. 根据权利要求10-13中任一项所述的联合方法，其特征在于，该联合方法还包含附加的微藻养殖步骤，其在初始阶段为该联合方法提供微藻，和/或在所述微藻养殖步骤(1)中的微藻需要补充时提供附加的微藻。
  15. 根据权利要求14所述的联合方法，其特征在于，该附加的微藻养殖步骤是与所述藻养殖步骤(1)分开的独立过程，以在需要时向所述藻养殖步骤(1)输入微藻。
  16. 根据权利要求14所述的联合方法，其特征在于，该附加的微藻养殖步骤合并入所述联合方法中，并处于所述藻养殖步骤(1)的上游。
  17. 用于养殖微藻和工业废气脱硝的联合方法的系统，其包含，任选从上游到下游地：
    NOx固定单元，用于对工业废气进行脱硝反应并提供固定了NOx的营养物流；
    微藻养殖器，用于利用所述固定了NOx的营养物流进行微藻养殖；
    分离器，用于将从微藻养殖器收获的藻液分离为藻泥和养殖残液； 加
    循环线路，用于将来自所述分离器的养殖残液循环回工艺上游，用于固定工业废气中的NOx；
    以及任选地，干燥器，用于干燥所述藻泥以得到微藻产品。
  18. 权利要求17所述的系统，其中所述NOx吸收单元具有含NOx的工业废气入口、养殖残液入口、固定了NOx的营养物流出口和净化后的工业废气出口；
    所述微藻养殖器具有固定了NOx的营养物流入口、藻种入口和藻液出口；
    所述分离器具有藻液入口、藻泥出口和养殖残液出口；和
    所述循环线路连接分离器的养殖残液出口和NOx吸收单元的养殖残液入口。
  19. 权利要求18所述的系统，其中所述NOx吸收单元包含脱硝反应器和NOx固定营养物流配制器。
  20. 根据权利要求18或19所述的系统，其特征在于，该系统还包含附加的微藻养殖设备，其在初始阶段为该系统提供微藻，和/或在所述微藻养殖器中的微藻需要补充时提供附加的微藻。
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