CN106032521B

CN106032521B - The method of cultivating microalgae and its with the united method of industrial waste gas denitration

Info

Publication number: CN106032521B
Application number: CN201510113349.0A
Authority: CN
Inventors: 荣峻峰; 朱俊英; 周旭华; 纪洪波
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-03-16
Filing date: 2015-03-16
Publication date: 2019-03-08
Anticipated expiration: 2035-03-16
Also published as: CN106032521A

Abstract

The present invention relates to the method for cultivating microalgae and its with the united method of industrial waste gas denitration, cultural method therein includes: in the culture medium of cultivating microalgae, and at least one of nitrogen source, phosphorus source and carbon source are provided in the form of alkali metal nutritive salt；In breeding process, the pH value of algae solution is adjusted with nitric acid and/or nitrous acid.The efficiency of cultivating microalgae can be improved using cultural method of the invention.

Description

The method of cultivating microalgae and its with the united method of industrial waste gas denitration

Technical field

The present invention relates to a kind of method of cultivating microalgae and a kind of cultivating microalgae and the united methods of industrial waste gas denitration.

Background technique

The energy " and " environment " are the major issues that new century human society in sustainable development is faced, on the one hand, branch The fossil energy of support mankind's modern civilization is non-renewable, thus countries in the world are stepping up to develop alternative energy source technology；It is another Aspect, the mankind are inevitably generated the emission problem of serious exhaust gas and sewage when processing and using fossil energy, to gas It waits and the living environment of the mankind has had resulted in serious influence.These problems need the solution made overall plans and coordinate.

Microalgae is " chemical plant living " of ultrahigh in efficiency driven by sunlight, by the efficient photosynthesis of microalgae cell, The chemical energy of the organic compounds such as fat or starch is converted light energy into, and releases O₂.Using microalgae production bioenergy and change Product can reach " substitution fossil energy and the discharge for reducing industrial waste gas " dual purpose simultaneously.

However, often there are many problems during the large-scale cultivation of microalgae, the hair of microalgae bioenergy is constrained Exhibition.Practice have shown that: the offer form of nitrogen source can seriously affect the effect of culture microalgae.If nitrogen source is provided in the form of ammonium salt, Then must be with lower concentration, usually less than 3.3mmol/L, otherwise the ammonium salt of high concentration can inhibit the growth of microalgae.In microalgae Nitrogen source can be provided for microalgae with amino acid during heterotrophism, but amino acid is expensive, economy is poor.Nitrate is micro- The nitrogen source being widely used in algae cultivation, but find in practice: the excessive concentration of nitrate can inhibit the growth of microalgae.Especially During microalgae luminous energy and feeding and chemoheterotrophy, demand of both breeding way to nitrogen source is larger, but in the medium Excessive nitrate is added, the growth of microalgae can't be remarkably promoted.

Nitrogen oxides (NOx) is one of main atmosphere pollution, can not only generate photochemical fog and acid rain, can also be led Cause serious greenhouse effects.The exhaust gas of industrial discharge is the main source of NOx in atmosphere, therefore the denitration problem day of industrial waste gas Benefit is valued by people.

The method of denitration of industrial waste gas can be divided into two kinds of dry and wet.Catalytic reduction method (SCR) and noncatalytic reduction It (SNCR) is common Dry denitration method, the investment of both methods and operating cost are higher, and NOx have been reduced into low The nitrogen of value does not achieve the purpose that resource utilization NOx.Wet denitration is that absorption is fixed in the NOx absorption in exhaust gas Method in liquid, the investment of such method and operating cost are low, but need to solve the problems, such as both sides, first is that in industrial waste gas NOx is mainly NO (typically constituting from 90% or more), and the extremely difficult water that is dissolved in of NO, it is therefore desirable to which the solubility for taking steps to solve NO is asked Topic；Second is that nitrous acid or nitrite are inevitably generated in absorption process, and nitrous acid or nitrite are hypertoxicity substances, therefore It needs to take measures to solve the problems, such as to separate or handle.

In suitable oxidizability (NO₂/ NO molar ratio) under, NOx can be fully absorbed with lye.1768902 A of CN is disclosed " use one or more of hydrogen peroxide, potassium permanganate, sodium chlorite, calcium hypochlorite, chlorine dioxide as oxidant, it will It after NO oxidation, then is absorbed with lye ".The study found that the effect is unsatisfactory by single hydrogenperoxide steam generator oxidation NO, however use A variety of oxidants aoxidize NO, so that liquid absorption element is become complicated, it may be difficult to carry out subsequent resource utilization.

102188891 A of CN discloses a kind of method that NOx is absorbed using concentrated nitric acid, two step of lye, and this method is by disappearing The NO that the concentrated nitric acid of consumption 2mol can aoxidize 1mol obtains the NO of 3mol₂, improve the oxidizability of NOx, then can be reached with lye To the effect for being completely fixed NO.However, can not only be consumed a large amount of if handling the mainly big capacity industrial waste gas containing NO with this method Nitric acid, and the NOx of nearly 3 times former contents will be generated in pilot process, therefore can also consume a large amount of alkali.In addition, should Method can generate a large amount of nitrite, how to separate, utilization or handle these toxic nitrite as problem.

Existing literature shows to use hydrogen peroxide/aqueous solution of nitric acid in the wet denitration method of absorbing liquid, effect compares There are two types of good, first is that absorbing the NOx of low degree of oxidation, such as USP using high concentration nitric acid/low concentration hydrogen peroxide aqueous solution The method referred in 4341747；Second is that absorbing low degree of oxidation using high-strength hydrogen peroxide/low concentration nitric acid aqueous solution The method referred in NOx, such as CN 102407068A.

Existing literature shows low concentration hydrogen peroxide/low concentration nitric acid aqueous solution to the absorptivity of low degree of oxidation NOx very It is low, therefore be not suitable for processing mainly containing the industrial waste gas of NO, such as " Effect of Temperature on NOx Absorption into Nitric Acid Solutions Containing Hydrogen Peroxide ", Ind.Eng.Chem.Res.1998,37,4418-4423。

The nitrogen source largely consumed is expensive for large-scale cultivation microalgae, if can be by cultivating microalgae and industrial waste gas Denitration combines, and can use NOx on the one hand as micro algae growth and provides nitrogenous fertilizer, to reduce the cost of cultivating microalgae；It is another The discharge that aspect can purify exhaust gas again, reduce NOx generates more overall situation benefit.It is existing that certain references disclose " by Industry Waste Gas is passed directly into both culturing microalgae device and carries out method of denitration ", however there is following insoluble problem in these methods: 1. utilize Microalgae, which carries out industrial waste gas denitration, must solve the problems, such as to limit its more commercialized, for example cultivating microalgae needs illumination and warm Weather conditions, and Changes in weather necessarily leads to the variation of microalgae denitration efficiency, and " being passed directly into industrial waste gas " will be difficult to match Exhaust gas discharges operating condition and both culturing microalgae operating condition, causes two-stage process to interact, is unable to satisfy the emission reduction requirement of actual production；② Nitric oxide (NO) is the main component of NOx, and the solubility of NO in water is extremely low, and therefore " being passed directly into industrial waste gas " can not Solve the problems, such as that a large amount of NO are not soluble in water and are difficult to absorb in NOx.

In general, photoautotrophic efficiency is less than 30g.m^-2.d^-1, the efficiency of outdoor large-scale culture is generally below 10g.m^- ².d^-1, a large amount of soil can be occupied by carrying out industrial waste gas denitration with such efficiency, it is therefore necessary to further increase microalgae Breeding efficiency.Addition organic carbon source carries out Heterotrophic culture or luminous energy and supports to be to accelerate the feasible method of micro algae growth, however adding After adding organic carbon source, algae solution easily by the pollution of harmful bacteria, causes the growth of bacterium to be significantly faster than the growth of microalgae, thus Both culturing microalgae is caused to fail.Using closed cultivation system and the achievable germ-free condition of stringent sterilizing is carried out, however for big For breeding scale microalgae, the cost of this method is prohibitively expensive.

Large-scale cultivation microalgae needs a large amount of water, if do not recycled to it, can greatly increase with water at This.In some cases, it is difficult to when being recycled to breeding water, for example using metal salt as nutrient source, cyclic culture water meeting It accumulates metal ion in breeding water body, its salinity is caused to be continuously increased, and high salinity usually has obviously the growth of microalgae Inhibiting effect.

Summary of the invention

The first purpose of this invention, which is that the breeding efficiency of raising microalgae, especially raising Heterotrophic culture and luminous energy are simultaneous, supports Breeding efficiency.Second object of the present invention is sterile working when avoiding Heterotrophic culture and luminous energy and supporting.Third of the invention A purpose is organically to combine both culturing microalgae with industrial waste gas denitration, can either provide nitrogen using NOx for micro algae growth Source, and influence each other caused by being avoided that due to exhaust gas discharge is different from both culturing microalgae operating condition.Fourth object of the present invention is, With nitric acid/hydrogen peroxide aqueous solution to industrial waste gas denitration, to avoid toxic nitrous acid is generated；The process is improved simultaneously Hydrogen peroxide utilization rate.

Specifically, the present invention includes the following contents.

1. a kind of method of cultivating microalgae, in the culture medium of cultivating microalgae, at least one of nitrogen source, phosphorus source and carbon source with The form of alkali metal nutritive salt provides, it is characterised in that；In breeding process, the pH value of algae solution is adjusted with nitric acid and/or nitrous acid.

2. according to method described in 1, which is characterized in that in the culture medium of cultivating microalgae, nitrogen source with alkali nitrates and/ Or the form of alkali metal nitrites salts provides.

3. according to method described in 1, which is characterized in that the breeding way of microalgae is Heterotrophic culture or luminous energy and supports.

4. according to method described in 3, which is characterized in that used organic carbon source be selected from sugar, organic acid, acylate, Alcohol, cellulose hydrolysate and at least one of with glucidtemns；It is preferred that glucose, fructose, acetic acid, sodium acetate, lactic acid, second At least one of alcohol, methanol and cellulose hydrolysate, more preferable glucose.

5. according to method described in 3, which is characterized in that the control of the concentration of used organic carbon source 1g/L algae solution~ 30g/L algae solution is preferably controlled in 2g/L algae solution~10g/L algae solution.

6. according to the method for claim 1, which is characterized in that when breeding way is photoautotrophy or luminous energy and supports, Light intensity is 1000~200000 luxs.

7. according to method described in 1, which is characterized in that further include isolating microalgae from the algae solution of harvest, and will separate The step of feeding algae raffinate circulation obtained after microalgae out is for cultivating microalgae.

8. according to method described in 3, which is characterized in that in breeding process, the EM bacterium (additional amount of EM bacterium is added into algae solution It is 1 × 10⁶A/algae solution~9 × 10 L⁸A/L algae solution, preferably 1 × 10⁷A/algae solution~5 × 10 L⁸A/L algae solution).

9. the integrated processes of a kind of cultivating microalgae and industrial waste gas denitration, comprising the following steps:

(1) the step of cultivating microalgae；In the step, in the culture medium of cultivating microalgae, in nitrogen source, phosphorus source and carbon source at least It is a kind of to be provided in the form of alkali metal nutritive salt；

(2) by the NOx conversion in industrial waste gas be nitric acid and/or nitrous acid the step of；

(3) nitric acid and/or nitrous acid obtained in step (2) is used, the algae solution pH value of breeding process in regulating step (1).

10. according to method described in 9, which is characterized in that in the culture medium of step (1), nitrogen source with alkali nitrates and/ Or the form of alkali metal nitrites salts provides.

11. according to method described in 9, which is characterized in that the breeding way of step (1) is Heterotrophic culture or luminous energy and supports.

12. according to method described in 11, which is characterized in that used organic carbon source is selected from sugar, organic acid, organic acid Salt, alcohol, cellulose hydrolysate and at least one of with glucidtemns；It is preferred that glucose, fructose, acetic acid, sodium acetate, cream At least one of acid, ethyl alcohol, methanol and cellulose hydrolysate, more preferable glucose.

13. according to method described in 11, which is characterized in that the control of the concentration of used organic carbon source 1g/L algae solution~ 30g/L algae solution is preferably controlled in 2g/L algae solution~10g/L algae solution.

14. according to method described in 9, which is characterized in that the breeding way of step (1) is photoautotrophy or luminous energy and supports When, light intensity is 1000~200000 luxs.

15. according to method described in 9, which is characterized in that in the breeding process of step (1), EM bacterium (EM is added into algae solution The additional amount of bacterium is 1 × 10⁶A/algae solution~9 × 10 L⁸A/L algae solution, preferably 1 × 10⁷A/algae solution~5 × 10 L⁸A/L algae Liquid).

16. according to method described in 9, which is characterized in that in step (2), using wet denitration by the NOx in industrial waste gas It is converted into nitric acid；Absorbing liquid in wet denitration is by the nitric acid of 0.5m%~58m%, the hydrogen peroxide of 0.001m%~25m% It is formed with excess water.

17. according to method described in 14, which is characterized in that absorbing liquid by by 10m%~25m% nitric acid, 0.1m%~ The hydrogen peroxide and excess water of 1m% forms.

The present invention achieves following technical effect.

According to the present invention, during cultivating microalgae, the pH value of algae solution is adjusted with nitric acid and/or nitrous acid, is mentioned significantly The high efficiency of cultivating microalgae.

According to the present invention, both culturing microalgae and industrial waste gas denitration are two relatively independent processes, are avoided because exhaust gas is arranged Put it is different from both culturing microalgae operating condition and caused by influence each other, it is not soluble in water and be difficult to the problem of absorbing to avoid a large amount of NO, no Need additional lye that can provide nitrogen source for microalgae using the NOx in industrial waste gas, this make method cultivation of the invention at This is lower.

The invention avoids the accumulation problems of metal ion, and breeding water body is enable to recycle.

According to the present invention, EM bacterium is added in algae solution, the breeding of harmful bacteria can be effectively inhibited, increased substantially micro- The growth rate of algae.This feature makes the present invention when Heterotrophic culture or luminous energy are simultaneous feeding, does not need the sterilizing that carries out disinfection, therefore make The present invention is with greater advantage.

According to the present invention, using the aqueous solution of low concentration hydrogen peroxide and low concentration nitric acid to industrial waste gas denitration, peroxide The resolution ratio of change hydrogen is lower, effective rate of utilization is very high.

According to the present invention, dust technology is produced while to industrial waste gas denitration, toxic nitrous is free of in the dust technology Acid is more advantageous to the nitrogen source for being used as cultivating microalgae.

Detailed description of the invention

Fig. 1 is chlorella growth curve.

Fig. 2 is growth of spirulina platensis curve.

Fig. 3 is the micro algae growth curve of embodiment 6~9 and comparative example 4.

Fig. 4 is the micro algae growth curve of embodiment 10~13.

Specific embodiment

A specific embodiment of the invention described further below, it should be noted however that protection scope of the present invention is not It is limited to these specific embodiments, but is determined by claims.

Unless otherwise defined, all technical and scientific terms used herein all has those skilled in the art conventional The meaning of understanding.In case of conflict, it is subject to the definition of this specification.

In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with It is freely combined with one or more other embodiments described herein, the technical solution or technical idea being consequently formed are accordingly to be regarded as A part of the original disclosure of the present invention or original description, and it is not considered as the new content for not disclosing or being expected herein, Unless those skilled in the art think that the combination is obvious unreasonable.

All features disclosed in this invention can in any combination, these combinations should be understood in disclosed in this invention Hold, unless those skilled in the art think that the combination is obviously unreasonable.Numerical point disclosed in this specification not only includes specific Disclosed numerical point further includes the endpoint of each numberical range, and the range of these numerical point institute any combination is regarded as this hair The bright range for disclosing or having recorded, no matter whether separately disclosing these numerical value pair herein.

(1) method of cultivating microalgae

A kind of method of cultivating microalgae, in the culture medium of cultivating microalgae, at least one of nitrogen source, phosphorus source and carbon source are with alkali The form of metal nutritive salt provides, it is characterised in that；In breeding process, the pH value of algae solution is adjusted with nitric acid and/or nitrous acid.

According to the present invention, breeding way can be photoautotrophy (under light illumination, merely with inorganic carbon source such as CO₂It is raw It is long), Heterotrophic culture (Heterotrophic culture refers to be grown merely with organic carbon source) or luminous energy and support that (luminous energy and supporting refers to, under light illumination Inorganic carbon source such as CO is utilized simultaneously₂It is grown with organic carbon source).

The necessary condition of micro algae growth needs, such as suitable temperature, sufficient illumination (photoautotrophy or luminous energy are simultaneous feeding), Enough water, CO₂And the nutriments such as nitrogenous fertilizer, phosphate fertilizer, regulate and control that dissolved oxygen in algae solution, pH value is in suitable range etc.. Although these conditions are not quite similar for different microalgaes, these are all known in the art.

In general, cultivation temperature is 15~40 DEG C, preferable temperature is 25~35 DEG C；Algae solution pH value is 6~11, preferably Algae solution pH value be 7~9.When photoautotrophy or simultaneous feeding luminous energy, light intensity is 1000~200000 luxs, and preferable light intensity is 5000~150000 luxs.

There is no limit for type of the present invention to microalgae., according to the invention it is preferred to cultivate those microalgaes for being suitable for oil-producing, in this way Not only bioenergy can be obtained, but also can be with exhaust gas emission reduction pollutant.

Although Heterotrophic culture or luminous energy and feeding meeting increase part aquaculture cost, breeding efficiency because using organic carbon source Also it greatly improves, is simplified following process process, so if can be avoided sterile cultivation, it will be able to avoid consumption a large amount of Steam carries out stringent sterilization processing to system, so that aquaculture cost be greatly reduced.According to the present invention, particularly preferably those can heterotrophism Culture or luminous energy and feeding microalgae, such as chlorella, scenedesmus, spirulina or single needle algae., it is surprising that with Heterotrophic culture or When luminous energy and feeding these microalgaes of mode culture, as long as a certain number of EM bacterium are added, even if cultivation also can without sterilization It goes on smoothly, the growth rate of microalgae is greatly speeded up, even if water source contains a large amount of harmful bacterias and/or opens wide cultivation, as a result It is such；And when being added without EM bacterium, Heterotrophic culture or simultaneous support of luminous energy usually will fail.

According to the present invention, it the Heterotrophic culture or luminous energy and supports, preferably without disinfecting action, is also added without sterilization Agent, but EM bacterium is added.

The EM bacterium (Effective Microorganisms) belongs to the prior art, mainly by belonging to photosynthetic bacteria Group, lactobacillus, yeast flora, Gram positive actinomycetes group, fermentation system Filamentous flora tens kinds of microorganism groups at being A kind of commercially available active bacteria formulation.The EM bacterium both can voluntarily prepare according to existing knowledge, can also be commercially available, and use It is preceding to need to illustrate to ferment according to having knowledge or commercial preparations.

According to the present invention, the dosage of EM bacterium should meet the needs for accelerating micro algae growth, can neither be very few without rising because of dosage Effect, and excessive nutriment cannot be consumed with microalgae competition due to dosage is excessive.The adding manner (such as one of any EM bacterium Secondary property is added or is added several times) and any EM bacterium dosage be all available, as long as being able to satisfy the needs for accelerating micro algae growth.

According to the present invention, the additional amount of EM bacterium is preferably 1 × 10⁶A/algae solution~9 × 10 L⁸A/L algae solution；More preferably 1 ×10⁷A/algae solution~5 × 10 L⁸A/L algae solution.

According to the present invention, when carrying out Heterotrophic culture or luminous energy and supporting, available organic carbon source includes but is not limited to sugared, organic At least one of acid, acylate, alcohol, cellulose hydrolysate and glucidtemns；For example it can be selected from glucose, fructose, second At least one of acid, sodium acetate, lactic acid, ethyl alcohol, methanol and cellulose hydrolysate, preferably selection is glucose.

According to the Expenditure Levels of nutriment in the growth pattern of micro algae biomass and culture solution, need to be replenished in time not The nutriment of foot.According to the present invention, any mode for adding nutriment is all available, for example segmentation is added or continuously mended Add, as long as can control the amount of nutriment in suitable range.

According to the present invention, when carrying out Heterotrophic culture or luminous energy and supporting, generally the concentration of organic carbon source is controlled in 1g/L algae Liquid~30g/L algae solution is preferably controlled in 2g/L algae solution~10g/L algae solution.Organic carbon source can be added at one time, and can also be divided more Secondary addition.

According to the present invention, in the alkali metal nutritive salt, metal ion is sodium and/or potassium.

According to the present invention, the nitrogen source is preferably alkali nitrates and/or alkali metal nitrites salts.

According to the present invention, the phosphorus source is preferably alkali metal phosphate and/or alkali metal hydrogen phosphate.

According to the present invention, a part of of the carbon source can be alkali carbonate and/or alkali metal hydrogencarbonate.

When according to the present invention, using photoautotrophy, carbon source wholly or largely is with CO₂Form provide.

According to the present invention, the nitrogen source, phosphorus source, the dosage of carbon source are provided by existing known technology, such as with nitrogen original Son meter, the dosage of nitrogen source are 0.1~400mmol/L, preferably 10~300mmol/L, still more preferably for 20~ 200mmol/L。

It according to the present invention, further include microalgae being isolated from the algae solution of harvest, and the feeding algae obtained after microalgae will be isolated The step of raffinate circulation is for cultivating microalgae.

(2) cultivating microalgae and the united method of industrial waste gas denitration

A kind of integrated processes of cultivating microalgae and industrial waste gas denitration, comprising the following steps:

The content of step (1) is identical as the method for aforementioned cultivating microalgae, and the present invention repeats no more.

According to the present invention, the NOx content in industrial waste gas is not particularly limited.In general, in industrial waste gas NOx content is differed in several hundred ppm (volume) to thousands of ppm, such as in 100ppm between 5000ppm.

According to the present invention, in the industrial waste gas, in terms of the total amount of NOx, molar fraction >=80% shared by NO；Into one Step, in the industrial waste gas, in terms of the total amount of NOx, molar fraction >=90% shared by NO.

According to the present invention, step (2) can be used any existing method by the NOx conversion in industrial waste gas be nitric acid and/ Or nitrous acid.

Some microalgaes can not be metabolized NO₂ ^-, when cultivating these microalgaes, the method for needing to select fixed NOx appropriate, with NOx is set largely or entirely to be converted into NO₃ ^-.According to the present invention, it is known that method appropriate is all available, such as with nitric acid/bis- Oxygen water is the oxidative absorption method of absorbent.

, according to the invention it is preferred to which NO can be metabolized simultaneously by cultivating those₃ ^-And NO₂ ^-Microalgae, such as the present invention filter out it is small Ball algae, single needle algae, scenedesmus or spirulina, there is no conversion NO at this time₂ ^-The problem of.

According to the present invention, in step (2), it is preferred to use the NOx conversion in industrial waste gas is nitric acid by wet denitration；Wet process Absorbing liquid in denitration is made of the nitric acid of 0.5m%~58m%, the hydrogen peroxide of 0.001m%~25m% and excess water.

The present inventor is the study found that although with high concentration nitric acid/low concentration hydrogen peroxide aqueous solution or highly concentrated spend Hydrogen oxide/low concentration nitric acid aqueous solution, can effectively absorb the NOx of low degree of oxidation, however both methods existed Hydrogen oxide decomposes very fast, the biggish defect of loss.In low concentration hydrogen peroxide/low concentration nitric acid aqueous solution, hydrogen peroxide Decomposition it is slower, however low concentration hydrogen peroxide/low concentration nitric acid aqueous solution is very low to the absorption activity of low degree of oxidation NOx. The present inventor has been surprisingly found that by further investigation, although in the initial stage, low concentration hydrogen peroxide/low concentration nitric acid aqueous solution It is very low to the absorption activity of low degree of oxidation NOx, but with the extension of time, the aqueous solution is active to the absorption of low degree of oxidation NOx It slowly increases, after a period of time, which enters high-caliber stationary phase to the absorption activity of low degree of oxidation NOx.

According to the present invention, in wet denitration above-mentioned, the absorbing liquid is preferably by the nitric acid of 10m%~25m%, 0.1m% The hydrogen peroxide and excess water of~1m% forms；More preferably by the peroxidating of the nitric acid of 10m%~25m%, 0.2m%~1m% Hydrogen and excess water composition.As previously mentioned, the initial denitration activity of the absorbing liquid of the composition is very low, it is necessary to the step activated by one Suddenly, just it is able to satisfy the requirement to industrial waste gas denitration.The activation step includes: will be by the nitric acid of 10m%~25m%, 0.1m% ~1m% hydrogen peroxide and excess water composition solution contacted with the gas containing NOx, when the solution denitration activity no longer When persistently rising, that is, complete activation step；In the gas containing NOx, in terms of the total amount of NOx, molar fraction shared by NO >= 80%.The gas containing NOx for activated absorption liquid can be the industrial waste gas.

According to the present invention, in wet denitration above-mentioned, denitration temperature can be -10 DEG C~40 DEG C, and denitration pressure can be 0.1Mpa~1Mpa；Preferred denitration temperature and pressure is room temperature (10 DEG C~40 DEG C) and normal pressure.

According to the present invention, the way of contact of industrial waste gas in aforementioned wet denitration and active absorption liquid is not limited particularly System, for example one of following (A), (B), (C) or its arbitrary combination can be used:

(A) industrial waste gas is dispersed in absorbing liquid with bubble shape；

(B) absorbing liquid is dispersed in industrial waste gas with droplet-like；

(C) liquid is contacted with membranaceous movement with industrial waste gas.

In preferred situation, using above-mentioned (A) mode.

According to the present invention, in the wet denitration, an absorption tower or multiple concatenated absorption towers can be used；It is preferred that adopting With an absorption tower or 2~3 concatenated absorption towers.The present invention is not particularly limited the type on absorption tower, for example can adopt With one of the following or its arbitrary combine: tray absorption columns, bubble absorbing tower, stirring bubble absorbing tower, by absorbing liquid with drop Spray tower, packed absorber and the film-falling absorption tower of shape dispersion in the gas phase；It is inhaled it is preferred that being bubbled using bubble absorbing tower or stirring Receive tower.

In the present invention, the denitration activity refers to that the NOx content for handling postindustrial exhaust gas accounts for and handles preceding industrial waste gas The molar fraction of NOx content.

Below by embodiment, the present invention will be described in detail.

Algae solution OD value (OD₆₈₀Value) measurement: OD value spectrophotometric determination is compared with distilled water, measurement Light absorption value of the algae solution at wavelength 680nm, the index as microalgae concentration.

The measurement of solution nitrogen content: using in ICS3000 type ion chromatograph (Dionex company, the U.S.) measurement aqueous solution NO₃ ^?Content or NO₂ ^-Content, instrument is equipped with EG40 leacheate automatic generator, electric conductivity detector and the work of chameleon chromatography It stands；IonPac AS11-HC type splitter (250mm × 4mmi.d.)；IonPac AG11 type guard column (50mm × 4mm i.d.)；Itself suppressor of ASRS-ULTRA anion.Leacheate: KOH solution；Flow velocity is 1mL/min；Eluent concentration: 30mmol/L；Sample volume is 60 μ L；Column temperature is 30 DEG C；Inhibit electric current 100mA；External standard method peak area quantification.

Count of bacteria: count of bacteria is carried out according to the following steps

1. sample washs: drawing 1ml sample, washed 2-3 times with 1 × PBS；2. initial gross separation: according to algae and bacterium from The difference of mental and physical efforts is centrifuged 2min, initial gross separation algae with 1000rpm first (for bacterium in supernatant, algae is in precipitating)；If When algae content is higher, repeat again；3. collecting supernatant, the amount of algae in supernatant is negligible at this time, 8000rpm centrifugation 5min abandons supernatant；4. precipitating is resuspended with the rupture of membranes agent of 500ul bacterium, 15min is reacted at room temperature；5.8000rpm is centrifuged 5min, with 1 × PBS washs 2 bacterium solutions；6. 1 × PBS of 100ul, which is added, is resuspended thallus, 5ul PI dye liquor mother liquor is added, reacts at room temperature 30min；7. Fluorescence microscopy microscopic observation bacterium simultaneously counts, and bacterial number is up to 1000 in 4 block plaids, when being greater than 1000, dilution Bacterium solution certain multiple counts again；8. calculation formula:

Bacterial density=count results/4 × extension rate × 4 × 10 in surveyed solution⁴A/ml

Main agents consumptive material:

Agents useful for same consumptive material	Manufacturer
		PI Viability Staining Solution	Four positive cypress Cat No.FXP002
Rupture of membranes agent	Sharp that health Cat No.REK3004
		Phosphate buffer (10 × PBS, pH7.4, cell culture grade are sterile)	Sharp that health Cat No.REK3013
Cell climbing sheet	NEST

Key instrument:

Instrument	Manufacturer
		Tally	Shanghai precision instrument
Fluorescence microscope	Olympus BX-51

The culture medium of microalgae: medium component is shown in Table 1~table 7.

1 culture medium BG11 of table

Component

Composition, mg/L

K₂HPO₄·3H₂O	40
		NaNO₃	1500
Na₂CO₃	20
		MgSO₄·7H₂O	75
CaCl₂·2H₂O	36
		Citric acid	6
Ferric citrate	6
		EDETATE SODIUM	1
Microelement A5 (table 2)	1

2 microelement A5 of table

Component	Composition, mg/L
		H₃BO₃	2860
MnCl₂·4H2O	1810
		ZnSO₄·7H₂O	222
CuSO₄·5H₂O	79
		NaMoO₄·5H₂O	390
Co(NO₃)₂·6H₂O	50

3 ZShi culture medium of table

Component	Composition, g/L
		KH₂PO₄·3H₂O	0.41
NaNO₃	2.5
		NaHCO₃	16.8

NaCl	1.0
		MgSO₄·7H₂O	0.20
K₂SO₄	1.0
		CaCl₂·2H₂O	0.04
FeSO₄·7H₂O	0.01
		EDETATE SODIUM	0.08
Microelement A5 (table 4)	1ml
		Microelement A6 (table 5)	1ml

4 microelement A5 of table

Component	Composition, g/L
		H₃BO₃	2.86
MnCl₂·4H₂O	1.8
		ZnSO₄·7H₂O	0.22
CuSO₄·5H2O	0.08
		MoO₃	0.01

5 microelement A6 of table

Component	Composition, mg/L
		NH₄VO₃	22.9
NiSO₃·7H₂O	47.8
		Ti₂(SO₄)₃	40
NaWO₄	17.9
		Co(NO₃)₂·6H₂O	4.4

6 Heterotrophic culture base of table

7 microelement of table

Component	Composition, g/L
		H₃BO₃	2.86
MnCl₂·4H₂O	0.11
		ZnSO₄·7H₂O	9.22
CuSO₄·5H₂O	1.00
		(NH₄)₆Mo₇O₂₄·4H₂O	0.10
Co(NO₃)₂·6H₂O	0.90

EM bacterium: probiotics used in embodiment is the production of the oasis Kang Yuan Biotechnology Co., Ltd such as golden probiotics, Illustrate to carry out activation processing, PH < 4 by it using preceding.

Comparative example 1

This comparative example is used for explanation low concentration NH₄HCO₃Cultivate the effect of chlorella.

Chlorella (offer of aquatile research institute, the Chinese Academy of Sciences) is cultivated using BG11 culture medium (table 1 and 2), BG11 is cultivated Nitrogen source in base is changed to NH₄HCO₃, nitrogen concentration 3.3mmol/L, the nitrogen concentration is dense far below the nitrogen source in BG11 culture medium It spends (17.6mmol/L).Algae initial concentration OD₆₈₀It is 0.5, is passed through compressed air culture, between 20~30 DEG C. Natural daylight culture is used in incubation, daylight intensity reaches as high as 60000lux.Its growth curve is shown in Fig. 1.

Comparative example 2

This comparative example is used for explanation low concentration NaNO₃Cultivate the effect of chlorella.

With the difference is that only for comparative example 1: the nitrogen source in culture medium is changed to NaNO₃.Algae solution is detected daily OD₆₈₀Value, growth curve are shown in Fig. 1.

Comparative example 3

This comparative example is for illustrating with high concentration NaNO₃Cultivate the effect of chlorella.

With comparative example 1 the difference is that: the nitrogen source in culture medium is changed to NaNO₃, nitrogen concentration increases to 176mmol/L, the nitrogen concentration is much higher than the nitrogen concentration (17.6mmol/L) in BG11 culture medium.Algae solution is detected daily OD₆₈₀Value, growth curve are shown in Fig. 1.

Embodiment 1

The present embodiment is used to illustrate effect of the present invention in autotrophy culture chlorella.

The present embodiment the difference is that only with comparative example 1: nitrogen source and its concentration still use the formula of BG11 culture medium, For late stage of culture when pH value is higher than 10, supplement nitric acid adjusts pH in suitable range, detects the OD of algae solution daily₆₈₀Value, Growth curve is shown in Fig. 1.

Embodiment 2

The present embodiment is used to illustrate effect of the present invention in autotrophy culture spirulina.

Using ZShi culture medium (table 3,4 and 5) cultivating spirulina (offer of aquatile research institute, the Chinese Academy of Sciences), algae starting Concentration OD₆₈₀It is 0.3, is passed through compressed air culture, between 20~30 DEG C, when pH value is higher than 10.5, supplements nitre Acid adjusts pH in suitable range.Natural daylight culture is used in incubation, daylight intensity reaches as high as 60000lux.The OD of detection algae solution daily₆₈₀Value, growth curve are shown in Fig. 2.

Embodiment 3

The present embodiment is used to illustrate effect of the present invention in mixotrophic cultivation chlorella (without disinfecting action).

The present embodiment the difference is that only with same comparative example 1: use chlorella heterotrophy culture medium (table 6 and 7), culture It adds 2g/L glucose and the fermented- EM bacterium solution of 0.5ml/L every three days in the process, when pH value is higher than 10, supplements nitric acid for pH Adjustment is in suitable range.The OD of detection algae solution daily₆₈₀Value, growth curve are shown in Fig. 1.

Embodiment 4

The present embodiment is used to illustrate effect of the present invention in mixotrophic cultivation spirulina (without disinfecting action).

The present embodiment the difference is that only with embodiment 2: in incubation, every three days add 2g/L glucose and The fermented- EM bacterium solution of 0.5ml/L, when pH value is higher than 10.5, supplement nitric acid adjusts pH in suitable range.Inspection daily Survey the OD of algae solution₆₈₀Value, growth curve are shown in Fig. 2.

Embodiment 5

The present embodiment is used to illustrate effect of the present invention in sterile Heterotrophic Mass Cultures of Chlorella.

Chlorella is identical as comparative example 1, carries out Heterotrophic culture, algae starting using chlorella heterotrophy culture medium (table 6 and 7) Concentration OD₆₈₀It is 0.5, is passed through compressed air, cultivated under sterile, no light condition, between 20~30 DEG C.Work as Portugal Grape sugar consumption totally when add glucose 10g/L in time；When pH value is higher than 10, supplement nitric acid adjusts pH in suitable range It is interior.The OD of detection algae solution daily₆₈₀Value, growth curve are shown in Fig. 1.

By Fig. 1~2 as it can be seen that using method of the invention, the growth efficiency of microalgae can be improved.If a large amount of at cultivation initial stage Nitrate is added, then high concentration nitrate can't remarkably promote the growth of microalgae.

Embodiment 6~13 is for illustrating that " in the case where largely addition organic carbon source, EM bacterium is metabolized microalgae inorganic nitrogen-sourced Influence ".

Embodiment 6

First using BG11 culture medium (adding nutritional ingredient by table 1,2, culture solution is without sterilization treatment) culture bead Algae (comes from Sinopec microalgae algae library, number Chlorella sp.RIPP-1)；Work as OD₆₈₀When value is 4, by 3 specified amount of table Add a Heterotrophic culture base nutritional ingredient.Between 20~30 DEG C, it is passed through compressed air and CO₂Culture, works as algae CO is passed through when liquid PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.Natural daylight culture, daylight are used in incubation Intensity reaches as high as 60000 luxs, adds the glucose of 2g/L, and press 2.9 × 10⁷The amount of a/L algae solution adds EM bacterium, often The OD of its detection algae solution₆₈₀Value；The glucose of 10g/L is added in culture again after 1 day, and presses 3.6 × 10⁷A/L algae solution adds EM Bacterium；Glucose 10g/L is added when culture was to the 5th day again, the count of bacteria that algae solution is monitored in breeding process is up to 9.7 × 10⁶A/mL algae solution, continuous culture harvest after 8 days, and last time stops being passed through CO after glucose is added₂, terminate algae solution when cultivation PH value is 8.6, is centrifugally separating to obtain algal gel and feeding algae raffinate.Analyze the NO supported in algae raffinate₃ ^?With NO₂ ^?Total content < 10 μ g/ g.The growth curve of microalgae is shown in Fig. 3.

Embodiment 7

The present embodiment and the difference of embodiment 6 are only that: culture microalgae is that single needle algae (comes from Sinopec microalgae algae Library, number Monoraphidium dybowskii.RIPP-50).The count of bacteria that algae solution is monitored in breeding process is up to 4.6 × 10⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 8.2 naturally, analyze the NO supported in algae raffinate₃ ^?With NO₂ ^?Total content < 200 μ g/g.The growth curve of microalgae is shown in Fig. 3.

Embodiment 8

The difference of the present embodiment and embodiment 6 is only that following aspect: the EM bacterium additive amount of first time is 7.9 × 10⁷A/ L algae solution does not add secondary EM bacterium；And second of glucose amount added is 30g/L, does not add third time glucose. It is up to 2.6 × 10 that the count of bacteria of algae solution is monitored in breeding process⁷A/mL algae solution measures the pH of algae solution at the end of cultivating certainly 8.2 are so increased to, the NO supported in algae raffinate is analyzed₃ ^?With NO₂ ^?Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 3.

Embodiment 9

The present embodiment and the difference of embodiment 8 are only that: culture microalgae is that single needle algae (comes from Sinopec microalgae algae Library, number Monoraphidium dybowskii.RIPP-50).The count of bacteria that algae solution is monitored in breeding process is up to 5.2 × 10⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 7.8 naturally, analyze the NO supported in algae raffinate₃ ^?With NO₂ ^?Total content < 200 μ g/g.The growth curve of microalgae is shown in Fig. 3.

Comparative example 4

The difference of this comparative example and embodiment 6 is only that: not adding EM bacterium.Monitor incubation in algae solution count of bacteria most A height of 13.6 × 10⁸A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 7.2 naturally.The growth curve of microalgae is shown in figure 3。

As can be seen from Fig. 3, addition EM bacterium is greatly facilitated the growth of microalgae and consumes rapidly inorganic nitrogen-sourced.

Embodiment 10

First using BG11 culture medium (adding nutritional ingredient by table 1,2, culture solution is without sterilization treatment) culture bead Algae；Work as OD₆₈₀When value is 4, a Heterotrophic culture base nutritional ingredient is added by 3 specified amount of table.Controlled at 20~30 DEG C it Between, it is passed through compressed air and CO₂Culture, is passed through CO as algae solution PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.It cultivated Natural daylight culture is used in journey, daylight intensity reaches as high as 60000 luxs, after chlorella inoculation first illumination from It is cultivated under the conditions of supporting 2 days, then adds the glucose of 2g/L, and press 1.8 × 10⁸The amount of a/L algae solution adds EM bacterium, examines daily Survey the OD of algae solution₆₈₀Value；The glucose of 10g/L is added in culture again after 3 days, and presses 1.8 × 10⁸A/L algae solution adds EM bacterium；Training Glucose 10g/L is added after supporting 2 days again, monitoring the count of bacteria of algae solution in breeding process is up to 2.9 × 10⁷A/mL algae Liquid, continuous culture harvest after 14 days, and last time stops being passed through CO after glucose is added₂, algae solution pH value is when terminating cultivation 9.2, it is centrifugally separating to obtain algal gel and feeding algae raffinate.Analyze the NO supported in algae raffinate₃ ^?With NO₂ ^?Total content < 10 μ g/g.Microalgae Growth curve see Fig. 4.

Embodiment 11

The difference of the present embodiment and embodiment 10 is only that following aspect: not adding secondary EM bacterium；And second The glucose amount of addition is 30g/L, does not add third time glucose.In breeding process monitor algae solution count of bacteria be up to 2.9×10⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 9.3 naturally, analyze the NO supported in algae raffinate₃ ^?With NO₂ ^?Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 4.

Embodiment 12

The present embodiment and the difference of embodiment 10 are only that: NaNO in BG11 culture medium₃Replace with KNO₃, and KNO₃Add Dosage is 0.5g/L.It is up to 1.3 × 10 that the count of bacteria of algae solution is monitored in breeding process⁷A/mL algae solution measures end cultivation When algae solution pH value be 9.4, analyze support algae raffinate in NO₃ ^?With NO₂ ^?Total content < 10 μ g/g.The growth curve of microalgae is shown in figure 4。

Embodiment 13

The present embodiment and the difference of embodiment 11 are only that: the NaNO in BG11 culture medium₃Replace with KNO₃, and KNO₃ Additive amount is 0.5g/L.It is up to 1.7 × 10 that the count of bacteria of algae solution is monitored in breeding process⁷A/mL algae solution measures end and supports The pH value of algae solution is 9.3 when growing, and analyzes and supports algae raffinate

In NO₃ ^?With NO₂ ^?Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 4.

As can be seen from Fig. 4, using potassium nitrate or sodium nitrate as nitrogen source, the growth that EM bacterium promotes microalgae is added.

Embodiment 14

The present embodiment is for illustrating nitric acid or H₂O₂Concentration changes the influence to hydrogen peroxide decomposition rate.

Prepare nitric acid/H of various concentration₂O₂Aqueous solution measured H after 10 days₂O₂Concentration, calculate the nitric acid of various concentration/ H₂O₂H in aqueous solution₂O₂Resolution ratio, calculated result are shown in Table 8.(measuring concentration of hydrogen peroxide with the method for GB1616-2003)

Table 8

No matter table 8 is as it can be seen that improve concentration of nitric acid, or improve concentration of hydrogen peroxide, the loss for resulting in hydrogen peroxide is aobvious It writes and increases.

Embodiment 15

The present embodiment is used to illustrate the present invention to the denitration effect of low concentration of NO x.

Simulated exhaust NO, NO₂It is prepared with nitrogen, the concentration of NO is 500ppm (volume), NO₂Concentration be 20ppm (body Product).Absorbing liquid is made of the nitric acid of 15m%, the hydrogen peroxide of 0.4m% and excess water.Absorption plant uses glass tower, glass Tower diameter is 100mm, a height of 700mm；It is equipped with sieve plate in the bottom of glass tower, hole diameter of sieve (perforated) plate is 16 μm~30 μm；Tower is provided with 3000ml absorbing liquid；The flow velocity of simulated exhaust is 150L/h；Test carries out under room temperature, normal pressure.Test result is shown in Table 9.It (uses The method of GB/T14642-2009 measures, without nitrite anions in the absorbing liquid after discovery test)

Table 9

For table 9 as it can be seen that in the denitration initial stage, the denitration activity of absorbing liquid is very low, increase with time, absorbing liquid denitration activity Slowly continue to increase, the denitration activity of absorbing liquid enters stationary phase after 16 hours, and denitrification rate at this time reaches 90% or more.

Embodiment 16

The present embodiment the difference is that only with embodiment 15: the concentration of hydrogen peroxide is 1m%, and the concentration of nitric acid is 25m%.Test result is shown in Table 10.It (is measured with the method for GB/T14642-2009, without nitrous acid in the absorbing liquid after discovery test Root)

Table 10

Time/h	1	2	4	8	12	16	20
								Export NO/ppm	430	400	330	220	100	36	27
Export NO₂/ppm	0	0	0	0	0	2	11
								Export NOx/ppm	430	400	330	220	100	38	38

Embodiment 17

The present embodiment is for illustrating, to the denitration effect of high concentrate NOx when the present invention uses single column.

The present embodiment the difference is that only with embodiment 15: the concentration of hydrogen peroxide is 0.3m%, the concentration of nitric acid For 15m%；In simulated exhaust, the concentration of NO is 3200ppm (volume), NO₂Concentration be 100ppm (volume).Test result is shown in Table 11.(being measured with the method for GB/T14642-2009, without nitrite anions in the absorbing liquid after discovery test)

Table 11

Time/h	1	2	4	8	12	16	20	24	30	35	40	45
													Export NO/ppm	2310	1900	1600	1400	1300	1250	1200	1000	830	750	800	830
Export NO₂/ppm	60	50	35	35	30	30	50	120	290	320	290	260
													Export NOx/ppm	2370	1950	1635	1435	1330	1280	1250	1120	1110	1070	1090	1090

Embodiment 18

The present embodiment uses high concentration H for illustrating₂O₂When denitration effect.

The present embodiment the difference is that only with embodiment 15: the concentration of hydrogen peroxide is 2.5m%, the concentration of nitric acid For 15m%.Test result is shown in Table 12.

Table 12

Time/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

Embodiment 19

This comparative example is used for denitration effect when illustrating using high concentration nitric acid.

This comparative example the difference is that only with embodiment 15: the concentration of hydrogen peroxide is 0.4m%, the concentration of nitric acid For 35m%.Test result is shown in Table 13.It is measured with the method for GB/T14642-2009, without nitrous in the absorbing liquid after discovery test Acid group.

Table 13

Time/h	1	2	4	8	12	16	20
								NO/ppm	57	6	11	9	9	10	11
NO₂/ppm	30	43	37	32	32	33	32
								NOx/ppm	87	49	48	41	41	43	43

Claims

1. a kind of method of cultivating microalgae, in the culture medium of cultivating microalgae, at least one of nitrogen source, phosphorus source and carbon source are with alkali gold The form for belonging to nutritive salt provides；It is characterized in that, breeding way is with CO₂For the photoautotrophy of carbon source, Heterotrophic culture or with CO₂ It is simultaneous feeding for the luminous energy of inorganic carbon source；In breeding process, the pH value of algae solution is adjusted with nitric acid and/or nitrous acid；

This method further includes microalgae being isolated from the algae solution of harvest, and use the feeding algae raffinate circulation obtained after microalgae is isolated In the cultivating microalgae the step of.

2. according to the method for claim 1, which is characterized in that in the culture medium of the cultivating microalgae, nitrogen source is with alkali metal The form of nitrate and/or alkali metal nitrites salts provides.

3. according to the method for claim 1, which is characterized in that the breeding way of microalgae is for Heterotrophic culture or with CO₂For carbon source Luminous energy and support when, without disinfecting action and be added without bactericidal agent, but be added EM bacterium.

4. according to the method for claim 3, which is characterized in that Heterotrophic culture or with CO₂It is simultaneous feeding for the luminous energy of inorganic carbon source When, used organic carbon source in sugar, organic acid, acylate, alcohol, cellulose hydrolysate and glucidtemns at least It is a kind of.

5. according to the method for claim 3, which is characterized in that Heterotrophic culture or with CO₂It is simultaneous feeding for the luminous energy of inorganic carbon source When, the concentration of used organic carbon source is controlled in 1g/L algae solution~30g/L algae solution.

6. according to the method for claim 1, which is characterized in that breeding way is with CO₂For inorganic carbon source photoautotrophy or With CO₂When simultaneous feeding for the luminous energy of inorganic carbon source, light intensity is 1000~200000 luxs.

7. according to the method for claim 1, which is characterized in that in breeding process, EM bacterium is added into algae solution.

8. according to method described in claim 3 or 7, which is characterized in that the additional amount of EM bacterium is 1 × 10⁶A/algae solution~9 L × 10⁸A/L algae solution.

(1) the step of cultivating microalgae；In the step, in the culture medium of cultivating microalgae, at least one of nitrogen source, phosphorus source and carbon source It is provided in the form of alkali metal nutritive salt；Breeding way is with CO₂For the photoautotrophy of carbon source, Heterotrophic culture or with CO₂It is inorganic The luminous energy of carbon source is simultaneous to support；

(3) nitric acid and/or nitrous acid obtained in step (2) is used, the algae solution pH value of breeding process in regulating step (1)；

10. according to the method for claim 9, which is characterized in that in the culture medium of the step (1), nitrogen source is with alkali metal The form of nitrate and/or alkali metal nitrites salts provides.

11. according to the method for claim 9, which is characterized in that the breeding way of step (1) is for Heterotrophic culture or with CO₂For When the luminous energy of carbon source is simultaneous feeding, without disinfecting action and it is added without bactericidal agent, but EM bacterium is added.

12. according to the method for claim 11, which is characterized in that breeding way is for Heterotrophic culture or with CO₂For inorganic carbon source Luminous energy and support when, used organic carbon source be selected from sugar, organic acid, acylate, alcohol, cellulose hydrolysate and and starch water Solve at least one of object.

13. according to the method for claim 11, which is characterized in that breeding way is for Heterotrophic culture or with CO₂For inorganic carbon source Luminous energy and when supporting, the concentration of used organic carbon source is controlled in 1g/L algae solution~30g/L algae solution.

14. according to the method for claim 9, which is characterized in that the breeding way of step (1) is with CO₂For inorganic carbon source Photoautotrophy or with CO₂When simultaneous feeding for the luminous energy of inorganic carbon source, light intensity is 1000~200000 luxs.

15. according to the method for claim 9, which is characterized in that in the breeding process of step (1), EM is added into algae solution Bacterium.

16. according to the method for claim 9, which is characterized in that, will be in industrial waste gas using wet denitration in step (2) NOx conversion be nitric acid；Absorbing liquid in wet denitration is by the nitric acid of 0.5m%~58m%, the hydrogen peroxide of 0.001m%~25m% It is formed with excess water.

17. according to the method for claim 16, which is characterized in that absorbing liquid by the nitric acid of 10m%~25m%, 0.1m%~ The hydrogen peroxide and excess water of 1m% forms；The absorbing liquid pass through an activation the step of, the activation step include: by by The solution of the nitric acid of 10m%~25m%, the hydrogen peroxide of 0.1m%~1m% and excess water composition is contacted with the gas containing NOx, works as institute When stating the denitration activity of solution and no longer persistently rising, i.e. completion activation step；In the industrial waste gas, in terms of the total amount of NOx, Molar fraction >=80% shared by NO.