CN105462842B - A kind of integrated processes of both culturing microalgae and industrial waste gas denitration - Google Patents
A kind of integrated processes of both culturing microalgae and industrial waste gas denitration Download PDFInfo
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- CN105462842B CN105462842B CN201410455398.8A CN201410455398A CN105462842B CN 105462842 B CN105462842 B CN 105462842B CN 201410455398 A CN201410455398 A CN 201410455398A CN 105462842 B CN105462842 B CN 105462842B
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Abstract
The present invention relates to the integrated processes of a kind of cultivating microalgae and industrial waste gas denitration, comprising: the step of Heterotrophic culture microalgae；The step of autotrophy culture microalgae；The step of microalgae is to obtain microalgae and alkaline residue is isolated from the algae solution of harvest；The NOx in industrial waste gas is absorbed using the alkaline residue or neutralizes the acid solution after fixing NOx, and the step of then providing nitrogen source with it for cultivating microalgae.The present invention utilizes the NO in industrial waste gasxNitrogen source is provided for cultivating microalgae, while pollutant emission reduction, obtains valuable microalgae biomass.
Description
Technical field
The present invention relates to the integrated processes of a kind of both culturing microalgae and exhaust gas denitration.
Background technique
Energy and environment are the major issues that human social is faced.On the one hand, the modern text of the support mankind
Bright fossil energy is non-renewable, and exploitation alternative energy source is extremely urgent；It on the other hand, can not when processing and using fossil energy
The emission problem of exhaust gas and sewage can be generated with avoiding, serious influence is caused on environment, these problems need system
Raise the solution of coordination.
Microalgae is many kinds of and the extremely extensive aquatic rudimentary plant of distribution.They pass through efficient photosynthesis, will
Luminous energy is converted into the chemical energy of the carbohydrate such as fat or starch, is known as " the activation factory of sunlight driving ".Utilize microalgae
Production bioenergy and chemicals are expected to reach the dual purpose of " substitution fossil energy, purification exhaust gas and sewage " simultaneously.
Nitrogen oxides (NOx) in industrial waste gas is one of main atmosphere pollution, can not only generate photochemistry cigarette
Mist and acid rain also result in serious greenhouse effects, are the main inducings of atmospheric haze, therefore the denitration problem day of industrial waste gas
Benefit is valued by people.Catalytic reduction method (SCR) and noncatalytic reduction (SNCR) are currently used exhaust gas denitration methods,
NOx is reduced into the nitrogen of low value by both methods, does not achieve the purpose that resource utilization NOx.Alkali absorption method
Process flow and equipment are relatively easy, and can be by NOx conversion at useful nitrite and/or nitrate, but this method
There are deficiencies below: concentration of lye cannot be too high, otherwise can crystallize during absorbing NOx, causes the stifled of absorption tower
Plug, and under low alkaline concentration, it necessarily will increase the energy consumption for extracting salt made from earth containing a comparatively high percentage of sodium chloride.Nitric acid absorption process is the exhaust gas of another kind of industrial application
Method of denitration, this method absorb NOx with aqueous solution of nitric acid, can obtain more nitric acid.Nitric acid absorption process is more suitable for nitric acid system
Enterprise is made, for other enterprises, there are problems for the economy of the storage of nitric acid and absorption technique.
Nitrogen is consumption most one of fast, the nutrient most easily lacked during micro algae growth.The nitrogenous fertilizer largely consumed is to feeding
It is expensive for growing for microalgae, if can combine cultivating microalgae with industrial waste gas denitration, on the one hand can use NOx is
Micro algae growth provides nitrogenous fertilizer, to reduce the cost of cultivating microalgae；On the other hand the discharge that exhaust gas can be purified again, reduce NOx,
Generate more overall situation benefit.It is existing that certain references disclose " industrial waste gas is passed directly into the side that both culturing microalgae device carries out denitration
Method ", however there is following insoluble problem in these methods: 1. carrying out industrial waste gas denitration using microalgae must solve to limit
Its commercialized some problem is made, for example cultivating microalgae needs illumination and warm weather conditions, and Changes in weather necessarily causes
The variation of microalgae denitration efficiency, " being passed directly into industrial waste gas " will be difficult to match exhaust gas discharge operating condition and both culturing microalgae operating condition, make
It interacts at two-stage process, 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, therefore " is passed directly into industrial waste gas " and can not solve a large amount of NO in NOx and is not soluble in water and difficult
The problem of to absorb.
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.In addition, will be unable to operate in illumination deficiency only with autotrophy culture, therefore there is a need to reduce overall process
To the dependence of illumination.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides the integrated processes of a kind of both culturing microalgae and industrial waste gas denitration.
A kind of integrated processes of both culturing microalgae and industrial waste gas denitration, comprising the following steps:
(1) the step of Heterotrophic culture microalgae；
(2) dilution step (1) algae solution obtained and photoautotrophic step is carried out；Make this step knot by microalgae metabolism
Algae solution when beam is in alkalinity；
(3) the step of isolating microalgae from the algae solution that step (2) harvest to obtain microalgae and alkaline residue；
With
(4) combination of one or both of following step (A), step (B)；
(A) NOx in industrial waste gas is absorbed with the alkaline residue that step (3) obtains, is step with the solution after absorption NOx
(1) the step of and/or the cultivating microalgae process of step (2) provides nitrogen source；
It (B) is nitric acid and/or nitrous acid, the alkaline residue that step (3) is obtained and institute by the NOx conversion in industrial waste gas
It states nitric acid and/or nitrous acid mixing, the microalga cultivation process with the mixed solution for step (1) and/or step (2) provides nitrogen source
The step of.
According to the present invention, for the microalgae, as long as can be carried out Heterotrophic culture and photoautotrophy, without its other party
The limitation in face.The present invention preferably cultivates those microalgaes for being suitable for oil-producing, can not only obtain bioenergy in this way, but also can be useless with emission reduction
Gas pollutant.
The necessary condition of micro algae growth needs, such as suitable temperature, sufficient illumination (photoautotrophy), 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 for not
Same microalgae, these conditions are not quite similar, but 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, light intensity is 1000~200000 luxs, and preferable light intensity is 5000~150000
Lux.
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.
Conventional Heterotrophic culture must carry out disinfecting action to culture environment, and not provide illumination.According to the present invention, it walks
Suddenly the Heterotrophic culture of (1) is two ways, a kind of identical as above-mentioned usual manner；Another area with above-mentioned usual manner
Offer illumination is not provided.In step (1), light intensity can be 1000~200000 luxs, preferable light intensity be 5000~
150000 luxs.
According to the present invention, in step (1), available organic carbon source include but is not limited to sugar, organic acid, acylate, alcohol,
At least one of cellulose hydrolysate and glucidtemns；Such as can be selected from glucose, fructose, acetic acid, sodium acetate, lactic acid,
At least one of ethyl alcohol, methanol, cellulose hydrolysate and cellulose hydrolysate.For general microalgae, glucose, second
Sour sodium or acetic acid are the organic carbon sources being very suitable for, wherein it is preferred that glucose.
The present inventor is had found by a large number of experiments, for photoautotrophic breeding way, when microalgae is metabolized alkali metal nitric acid
One of salt, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate
Or any combination thereof when, if not being passed through CO into algae solution in the breeding process of microalgae2Or pH adjusting agent, then the pH value of algae solution
It can rise, especially when microalgae metabolism alkali nitrates, alkali metal nitrites salts or combinations thereof (than passing through regular worker as the aforementioned
NOx in industry exhaust gas and the nitrogen source obtained) when, faster ascendant trend is presented in algae solution pH value.The pH value of general cultivating microalgae is 6
~11, when culture solution contains above-mentioned nutriment, in order to avoid the pH value of culture solution exceeds the permitted range of micro algae growth,
By controlling CO2Or the additional amount of pH adjusting agent, the pH value of algae solution is controlled in suitable range with can be convenient.
It is golden when containing alkali nitrates, alkali in the culture solution of microalgae as described previously for photoautotrophic breeding way
One of genus nitrosomonas salt, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate or its
When meaning combination, if not providing or providing less CO in the breeding process of microalgae2Or pH adjusting agent, then the pH value of algae solution is presented
The trend of rising.Utilize this phenomenon, so that it may in the cultivating microalgae later period, not provide or provide less CO2Or pH adjusting agent, it relies on
Microalgae, which is metabolized alkali metal nutritive salt above-mentioned, makes the algae solution at the end of cultivation in alkalinity, thus can use and isolates microalgae
Alkaline residue absorbs the NOx in exhaust gas or neutralizes the acid solution after fixed NOx, and necessary to then be provided with it for cultivating microalgae
Nitrogen source.
According to the present invention, in step (2), in the cultivating microalgae later period, do not provide or provide less CO2(or pH adjusting agent), according to
Make the algae solution at the end of cultivation in alkalinity by microalgae metabolism alkali metal nutritive salt；The alkali metal nutritive salt is alkali metal nitric acid
One of salt, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate
Or any combination thereof.Various alkali metal nutritive salt above-mentioned are preferably sodium salt and/or sylvite.
According to the present invention, in step (2), preferably relying upon microalgae metabolism makes pH value > 8 of algae solution at the end of cultivating, more preferably
Make the pH value 9~11 of algae solution at the end of cultivating by microalgae metabolism.
Make us unexpected, compared with the lye of preparation, the alkaline residue after isolating microalgae is in industrial waste gas
NOx have higher absorption efficiency.The NOx in industrial waste gas is absorbed using alkaline residue or neutralizes the acid after fixing NOx
Liquid, it is available to contain NO3 -And/or NO2 -Solution, which directly can provide nitrogen source for next group both culturing microalgae, the nitrogen
After source is metabolized by microalgae, algae solution can be made in alkalinity again, one mode can be in both culturing microalgae culture solution and industry in this way
Closed circulation is realized between the absorbing liquid or neutralizer of exhaust gas denitration process, thus by " both culturing microalgae " and " Industry Waste qi exhaustion
Nitre " organically connects, and not only can use microalgae and nitrogen pollutant is expeditiously converted to useful biomass, but also make
" both culturing microalgae " and " exhaust gas denitration " becomes two relatively independent processes, avoids influencing each other for the two.
Alkali absorption method is a kind of exhaust gas denitration technique of maturation, absorbs grinding for exhaust gas NOx about using alkaline aqueous solution
Study carefully also very much, the present invention can be using any one of these existing methods.It is known that in order to absorb NO completely, it can be
Lye adds oxidizing tower before absorption tower, using in exhaust gas remaining oxygen or addition ozone NO is oxidized to NO2, mentioned for alkali absorption method
For optimum oxidizability (NO2/ NO molar ratio).Catalyst for catalytic oxidation suitable for different situations be all it is known in the art,
It for example with active carbon, activated carbon fiber, high silicon Na-ZSM-5 molecular sieve or total silicon beta-molecular sieve is catalyst at normal temperature by NO oxygen
It is melted into NO2。
According to the present invention, step (A) absorbs fixed NOx using alkali absorption method, for absorbing the absorption of fixed exhaust gas NOx
Liquid is not provided with the extraction salt made from earth containing a comparatively high percentage of sodium chloride step of these existing soda liquor absorption techniques using the alkaline residue obtained in microalga cultivation process
Suddenly, but by the solution obtained after NOx is absorbed nitrogen source directly is provided for cultivating microalgae.
According to the present invention, step (B) can be used any existing method by the NOx conversion in industrial waste gas be nitric acid and/
Or nitrous acid, such as nitric acid absorption process or the method for fixing NOx with nitrifier.
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 be all available, such as with higher concentration nitric acid
Oxidative absorption method for absorbent or the method for fixing NOx with nitrifier.
, 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.
It according to the present invention, is preferably nitric acid and optional nitrous acid by the NOx conversion in industrial waste gas in step (B).
, according to the invention it is preferred to be resistant to the microalgae of high alkali environment, cultivating these microalgaes can be further improved alkalinity
The pH value of raffinate, and then improve with nitric acid and/or nitrite reaction or absorb the efficiency of NOx.Inventor passes through a large number of experiments,
Filter out the following microalgae that can be resistant to high alkali environment, such as chlorella, single needle algae, scenedesmus or spirulina, these microalgaes can be
PH is healthy growth in the environment of 9~11.
, according to the invention it is preferred to which those be not passed through CO2Or algae can be improved rapidly by own metabolism when pH adjusting agent
The microalgae of liquid pH value, cultivating these microalgaes can be further improved the efficiency of cultivating microalgae process.Inventor passes through a large number of experiments,
The following microalgae that can improve algae solution pH value rapidly is filtered out, such as chlorella, single needle algae, scenedesmus or spirulina, above-mentioned microalgae
The pH value of algae solution can be increased to 9~11 in 1~24 hour, make algae solution meet efficiently with nitric acid and/or nitrite reaction
Or absorb the requirement of fixed NOx.
It is that microalgae is provided in the solution of nitrogen source described in step (3) in preferred situation, in terms of nitrogen-atoms, nitrogen
The amount for closing object is 90~30000 μ g/g, preferably 500~20000 μ g/g.
In industrial waste gas other than containing NOx, it may also contain other pollutants such as SOx, those skilled in the art are logical
Cross simple test (such as variation degree by measurement NOx absorptivity or measurement micro algae growth rate), it will be able to confirm
Whether contain in exhaust gas or excessively containing the pollutant made a significant impact on integrated processes of the invention.Invention human hair
It is existing, when the SOx content in the flue gas of industrial discharge is higher, the feeding algae raffinate of alkalinity can be reduced to the absorption efficiency of NOx.According to need
It wants, the SOx in exhaust gas can also be reduced to by conventionally known technological means and not significantly affect this by those skilled in the art
The level that the integrated processes of invention are implemented.The flue gas of general industry discharge, contains a large amount of SOx, therefore especially in coal-fired flue-gas
For these industrial waste gases, the SOx contained before exhaust gas denitration of the invention is needed to remove.
According to the present invention, the industrial waste gas does not contain SOx preferably or by desulfurization process (in removing exhaust gas
SOx industrial waste gas).
The present invention is preferably with containing CO2Inorganic carbon source of the gas as step (2).
It should be appreciated that " both culturing microalgae " and " industrial waste gas denitration " in the present invention is two relatively independent processes,
It is described to contain CO2The major function of gas is to provide carbon source for micro algae growth, is substantially free of SOx and NOx.It is described to contain CO2Gas
Body can be the industrial waste gas by purified treatment (removing exhaust gas in SOx and NOx), or be the work without containing SOx and NOx
Industry exhaust gas.
The present invention achieves following technical effect.
According to the present invention, dependence inorganic nitrogen-sourced and that reduction is to illumination is quickly on the one hand consumed by Heterotrophic culture,
Achieve the purpose that improve denitration efficiency, reduces land occupation, improves stable technical process；On the other hand it is obtained by the way that Heterotrophic culture is quick
A large amount of microalgae algaes of autotrophy culture have been arrived, have then been absorbed in fixed exhaust gas by photoautotrophy using free sunlight again
NOx and CO2, produce valuable microalgae biomass.
According to the present invention, it is higher to the NOx absorption efficiency in industrial waste gas to support the feeding algae raffinate of alkalinity caused by algae.
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, this
Two processes are connected by the alkaline residue of microalgae, do not need additional alkaline absorption solution or alkaline neutralizer energy
Nitrogen source is provided for microalgae using the NOx in industrial waste gas, this makes method aquaculture cost of the invention lower.
According to the present invention, specific microalgae, such as chlorella, scenedesmus, single needle algae or spirulina, they can be metabolized simultaneously
NO3-And NO2-, the environment of high nitrogen concentration can be resistant to, moreover it is possible to which the metabolism by itself improves rapidly the pH of algae solution in the cultivation later period
Value, cultivating these microalgaes can be further improved the efficiency of conversion NOx.
According to the present invention, the processing step for simplifying industrial waste gas denitration improves the economy of its technical process, than
Such as, for alkali absorption method, additional alkaline absorption solution and salt made from earth containing a comparatively high percentage of sodium chloride extraction step are not needed；For NOx to be fixed as to the side of acid
Method does not need large-scale storage sour container, at the same do not need additional alkaline neutralizer nitric acid/nitrous acid can be converted to it is higher
The salt made from earth containing a comparatively high percentage of sodium chloride of value is used in cultivating microalgae.
The present invention has constructed the Mode of Circular of a kind of emission reduction industrial waste gas pollutant and production microalgae biomass.It utilizes
NO in the exhaust gas of industrial dischargexAs the nitrogen source in culture solution, while pollutant emission reduction, obtain valuable micro-
Algal biomass.In the mode of such a circular economy, the departmental cost of industrial waste gas is administered for cultivating microalgae, factory subtracts
Exhaust gas, discharge of wastewater and the pollution to environment are lacked, have formd closed circulation, outlet only has microalgae biomass.
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.
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
Bright published range, no matter whether separately disclosing these numerical value pair herein.
Detailed description of the invention
Fig. 1 is a kind of schematic diagram of preferred embodiment of the present invention.
Fig. 2 is the schematic diagram of denitrating technique.
Fig. 3~4 are the micro algae growth curve of embodiment 1.
Fig. 5~6 are the micro algae growth curve of embodiment 2.
Fig. 7 is the micro algae growth curve of embodiment 3.
Fig. 8~9 are the micro algae growth curve of embodiment 4.
Figure 10~11 are the micro algae growth curve of embodiment 5.
Figure 12 is the micro algae growth curve of embodiment 6.
Figure 13 is the micro algae growth curve of embodiment 7.
Specific embodiment
With embodiment, the present invention will be described in detail below, but is not therefore construed as limiting the invention.
Algae solution OD value (OD680Value) measurement:
OD value spectrophotometric determination, is compared with distilled water, measures extinction of the algae solution at wavelength 680nm
Value, the index as microalgae concentration.
The culture medium of microalgae:
Media Components are shown in Table 1~table 2.
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 | 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 |
The measurement of solution nitrogen content
Using the NO in ICS3000 type ion chromatograph (Dionex company, the U.S.) measurement aqueous solution3 ?Content or NO2 -
Content, instrument are furnished with EG40 leacheate automatic generator, electric conductivity detector and chameleon chromatographic work station；IonPac AS11-HC
Type splitter (250mm × 4mm i.d.)；IonPac AG11 type guard column (50mm × 4mm i.d.)；ASRS-ULTRA yin from
Itself sub suppressor.Leacheate: KOH solution；Flow velocity is 1mLmin-1；Eluent concentration: 30mmolL-1；Sample volume is 60
μL；Column temperature is 30 DEG C；Inhibit electric current 100mA；External standard method peak area quantification.
Embodiment 1
Microalgae Heterotrophic culture: use lighttight automatically controlled fermentor progress chlorella (Sinopec microalgae algae library is come from,
Number Chlorella sp.RIPP-1) Heterotrophic culture, culture medium be BG11 culture medium (table 1) in add glucose (glucose
Concentration 30g/L), NaNO in algae solution3Content is 17.6mmol/L, and controlled at 28 DEG C, algae initial concentration is OD680=
1.1, it is passed through compressed air (0.08MPa) and is cultivated, the ventilatory capacity of every liter of culture medium is 1L/min, and speed of agitator is
200rpm makes pH 6.9~7.1 using 2M KOH solution and 70% acetic acid solution automatic adjustment medium pH value, is added 0.1%
(v/v) defoaming agent (GPE) and 0.01g/L chloramphenicol prevent foam generation and living contaminants.The OD of daily sample detection algae solution680
Value.Measure concentration of residual glucose and NO in culture solution3 -Content, according to glucose and NaNO3Expenditure Levels carry out feed supplement, make to train
It is 30g/L that concentration of glucose is maintained in nutrient solution, maintains NO3 -Content is 1000~1500 μ g/g.Continuous culture stops mending after 4 days
Material harvests after continuing culture 2 days, and micro algae biomass growth is extremely rapid, remains NO at the end of culture in algae solution3 -Content is 300 μ
g/g.The heterotrophic growth curve of the present embodiment is shown in Fig. 3.
Microalgae autotrophy culture: the microalgae of above-mentioned Heterotrophic culture is transferred to small-sized raceway pond, and algae solution is centainly diluted
The autotrophy culture of microalgae light is carried out afterwards, and no longer addition culture medium, algae initial concentration are diluted to OD680It is 0.5, controlled at 20
Between~30 DEG C.Natural daylight culture is used in incubation, daylight intensity reaches as high as 60000 luxs, examines daily
Survey the OD of algae solution680Value.Continuous culture harvests after 7 days, and the algae solution pH at the end of detection culture is increased to 10.5 naturally, centrifugation point
From obtaining algal gel and feeding algae raffinate.The autophyting growth curve of the present embodiment is shown in Fig. 4.
It utilizes cultivation raffinate denitration: using NO2Industrial waste gas is simulated with the gaseous mixture of NO, wherein NO content is 450ppm
(v), NO2Content is 30ppm (v), and using compressed air as carrier gas, " acid+alkali " two-step method process absorbs NOx, and flow chart is shown in Fig. 2,
Wherein acid tower diameter 100mm, high 700mm, wherein the nitric acid 3L of 30m% is held, washing tower (for removing CO2) diameter 100mm, high 100mm, wherein containing
Put the feeding algae raffinate of the pH=10.5 of the generation of 3L embodiment 1.Total gas flow rate is 150L/h when operation, as the pH of washing tower (for removing CO2) tower bottom liquid
It is stopped operation when < 7.5, tower bottom liquid is taken out, measure NO therein3 ?With NO2 ?Total content be 4700 μ g/g.
Embodiment 2
The present embodiment is different from that of the embodiment 1 only in the following aspects: the washing tower (for removing CO2) tower bottom liquid (NO with embodiment 13 ?With NO2 ?It is total
Content is 4700 μ g/g) prepare micro algae culturing liquid.The heterotrophic growth curve of the present embodiment is shown in that Fig. 5, autophyting growth curve are shown in Fig. 6.
Embodiment 3
The present embodiment be different from that of the embodiment 1 only in the following aspects: the autotrophy stage continuously cultivate 10 days after harvest.The present embodiment
Autophyting growth curve see Fig. 7.
Algae solution pH at the end of the detection autotrophy stage is increased to 11.0 naturally.In the denitration stage, when tower bottom liquid pH is 7.5,
Detect NO in washing tower (for removing CO2) tower bottom liquid3 ?With NO2 -Total content be 5300 μ g/g, which can be re-used for the cultivation of microalgae.
Embodiment 4
The controlled concentration that the present embodiment is different from that of the embodiment 1 only in the following aspects: heterotrophism phasic change nitrate anion is 1500
~2000 μ g/g.The heterotrophic growth curve of the present embodiment is shown in that Fig. 8, autophyting growth curve are shown in Fig. 9.
Remaining NO in algae solution at the end of detection heterotrophism3 -Content is 470 μ g/g.Algae solution pH at the end of detection autotrophy is certainly
So it is increased to 9.9.In the denitration stage, when washing tower (for removing CO2) tower bottom liquid pH is 7.4, NO in washing tower (for removing CO2) tower bottom liquid is detected3 ?With NO2 -Total content
For 6400 μ g/g, which can be re-used for the cultivation of microalgae.
Embodiment 5
The present embodiment the difference is that only with embodiment 4: with the washing tower (for removing CO2) tower bottom liquid (NO of embodiment 43 ?With NO2 ?It is total
Content is 6400 μ g/g) micro algae culturing liquid is prepared, and cultivate single needle algae.The heterotrophic growth curve of the present embodiment is shown in Figure 10, from
Feeding growth curve is shown in Figure 11.
Embodiment 6
The present embodiment is different from that of the embodiment 1 only in the following aspects: using glass transmission fermentor Heterotrophic culture 4 under light illumination
Stop feed supplement after it, then continues culture 4 days under light illumination, detect that glucose is depleted in algae solution at this time, then again
Continue culture 4 days under light illumination, intensity of illumination is 8000 luxs.Microalgae is centrifugated, the pH value for detecting feeding algae raffinate is
8.7.NOx in tail gas is absorbed in experimental provision using feeding algae raffinate, tower bottom liquid pH is stopped operation when being 7.3, detects tower bottom liquid
Middle NO3 ?With NO2 -Total content be 6200 μ g/g.The heterotrophic growth curve of the present embodiment is shown in Figure 12.
Embodiment 7
The present embodiment the difference is that only with embodiment 6: with the washing tower (for removing CO2) tower bottom liquid (NO of embodiment 63 ?With NO2 ?It is total
Content is 6200 μ g/g) prepare micro algae culturing liquid.The heterotrophic growth curve of the present embodiment is shown in Figure 13.
Embodiment 8
The present embodiment absorbs NOx with the feeding algae raffinate of alkalinity for illustrating.
The alkalinity of Example 4 supports algae raffinate 3L；The sodium ion and potassium concentration in the feeding algae raffinate of the alkalinity are analyzed, is matched
System is HCO with its aqueous solution 3L with identical Na ion concentration and potassium concentration, pairing anion3 -And CO3 2-, prepared
PH value of water solution be 9.87, the pH value for supporting algae raffinate with the alkalinity of embodiment 4 is essentially identical.Algae is supported with above-mentioned alkalinity respectively
Raffinate and the aqueous solution of preparation are absorbing liquid, as a result, it has been found that: pact of the feeding algae raffinate of alkalinity to the absorptivity of NOx than obtained aqueous solution
It is high by 15~25%.
Comparative example 1
The present embodiment, which is different from that of the embodiment 1 only in the following aspects:, uses ammonium nitrate as nitrogen source, concentration 16mmol/L.Knot
Fruit discovery chlorella is unable to normal growth and dead, therefore can not carry out subsequent step.
Comparative example 2
The present embodiment is different from that of the embodiment 1 only in the following aspects: without photoautotrophy step.At the end of detecting heterotrophism
The pH of algae solution is 7.1, the NOx in simulated exhaust is absorbed with the feeding algae raffinate of acquisition, as a result, it has been found that absorption efficiency is very low, in solution
NO3 ?With NO2 -Total content be only 70 μ g/g, it is difficult to meet the needs of the normal fast-growth of microalgae.
By Examples 1 to 8 as it can be seen that using method of the invention, the alkaline residue that both can use cultivating microalgae is effectively inhaled
The NOx in industrial waste gas is received, and can use the absorbing liquid after absorbing NOx and normal quickly cultivation is carried out to microalgae.
Claims (12)
1. the integrated processes of a kind of both culturing microalgae and industrial waste gas denitration, comprising the following steps:
(1) the step of Heterotrophic culture microalgae；
(2) dilution step (1) algae solution obtained and photoautotrophic step is carried out；At the end of making this step by microalgae metabolism
Algae solution in alkalinity；With containing CO2Inorganic carbon source of the gas as this step；
(3) the step of isolating microalgae from the algae solution that step (2) harvest to obtain microalgae and alkaline residue；With
(4) combination of following step (B) or step (A) and step (B)；
(A) NOx in industrial waste gas is absorbed with the alkaline residue that step (3) obtains, is step (1) with the solution after absorption NOx
And/or the cultivating microalgae process of step (2) provides the step of nitrogen source；
It (B) is nitric acid and/or nitrous acid, the alkaline residue that step (3) is obtained and the nitre by the NOx conversion in industrial waste gas
Acid and/or nitrous acid mixing, the microalga cultivation process with the mixed solution for step (1) and/or step (2) provide the step of nitrogen source
Suddenly.
2. according to the method for claim 1, which is characterized in that in step (1) and/or step (2), cultivation temperature be 15~
40 DEG C, algae solution pH value is 6~11；In step (2), light intensity is 1000~200000 luxs.
3. according to the method for claim 2, which is characterized in that in step (1) and/or step (2), cultivation temperature be 25~
35 DEG C, algae solution pH value is 7~9；In step (2), light intensity is 5000~150000 luxs.
4. according to the method for claim 1, which is characterized in that in step (1), the organic carbon source used is selected from sugared, organic
At least one of acid, acylate, alcohol, cellulose hydrolysate and glucidtemns.
5. according to the method for claim 4, which is characterized in that in step (1), the organic carbon source that uses be selected from glucose,
At least one of fructose, acetic acid, sodium acetate, lactic acid, ethyl alcohol, methanol and cellulose hydrolysate.
6. according to the method for claim 1, which is characterized in that in step (2), make algae at the end of cultivating by microalgae metabolism
PH value > 8 of liquid.
7. according to the method for claim 6, which is characterized in that in step (2), make algae at the end of cultivating by microalgae metabolism
The pH value of liquid is 9~11.
8. according to the method for claim 1, which is characterized in that the microalgae is chlorella, single needle algae, scenedesmus or spiral
Algae.
9. according to the method for claim 1, which is characterized in that in step (4), provided in the solution of nitrogen source for microalgae, with
Nitrogen-atoms meter, the amount of nitrogenous compound are 90~30000 μ g/g.
10. according to the method for claim 9, which is characterized in that in step (4), provided in the solution of nitrogen source for microalgae, with
Nitrogen-atoms meter, the amount of nitrogenous compound are 500~20000 μ g/g.
11. according to the method for claim 1, which is characterized in that in step (4), the industrial waste gas is without containing SOx
Or the industrial waste gas Jing Guo desulfurization process.
12. according to the method for claim 1, which is characterized in that in step (2), in the cultivating microalgae later period, do not provide or few
CO is provided2, make the algae solution at the end of cultivation in alkalinity by microalgae metabolism alkali metal nutritive salt；The alkali metal nutritive salt is
One of alkali nitrates, alkali metal nitrites salts, alkali metal phosphate, alkali metal hydrogen phosphate or any combination thereof.
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