CN105985909B

CN105985909B - A kind of integrated processes and system producing microalgae biomass Yu industrial waste gas denitration

Info

Publication number: CN105985909B
Application number: CN201510046935.8A
Authority: CN
Inventors: 荣峻峰; 朱俊英; 纪洪波; 周旭华; 黄绪耕
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2015-01-29
Filing date: 2015-01-29
Publication date: 2019-11-15
Anticipated expiration: 2035-01-29
Also published as: CN105985909A

Abstract

The present invention relates to a kind of integrated processes and system for producing microalgae biomass Yu industrial waste gas denitration, the step of method therein includes: (1) cultivating microalgae；(2) the step of microalgae is to obtain microalgae and alkaline residue is isolated from algae solution；(3) the step of biomass is extracted from microalgae；It (4) is salt made from earth containing a comparatively high percentage of sodium chloride, and the step of providing nitrogen source with it for microalga cultivation process by the NOx conversion in industrial waste gas using alkaline residue.The present invention has constructed the Mode of Circular of a kind of emission reduction industrial waste gas pollutant and production microalgae biomass.

Description

A kind of integrated processes and system producing microalgae biomass Yu industrial waste gas denitration

Technical field

The present invention relates to a kind of integrated processes and system for producing microalgae biomass Yu industrial waste gas denitration.

Background technique

Energy and environment are the important topics 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；Generated exhaust gas when on the other hand, using fossil energy With sewage, serious influence is caused on environment, these problems need the solution made overall plans and coordinate.

The aquatic rudimentary plant that microalgae is many kinds of and distributed pole is wide, they are by efficient photosynthesis, by luminous energy It is converted into the chemical energy of the carbohydrate such as fat or starch, is known as " the activation factory of sunlight driving ".It is produced using microalgae 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 both culturing microalgae device and carries out denitration side 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.

There is complicated ecological relationships in nature, between microalgae and bacterium may for specific microalgae and bacterium It mutually promotes, it is also possible to mutually inhibit.Difficulty known to one of cultivating microalgae is that it is thin to there is a large amount of nocuousness in water and air Bacterium, these harmful bacterias are unfavorable for the growth of microalgae, will lead to cultivation failure when serious.When using open system cultivating microalgae, It can not be achieved germ-free condition, the risk being contaminated by bacterial is higher；Using closed cultivation system and carry out stringent sterilizing can Realize germ-free condition, however for large-scale farming microalgae, the cost of this method is prohibitively expensive.

Amount of NOx caused by chemical engineering industry is huge, if fixing the NOx in industrial waste gas with microalgae, it is necessary to make The rate of the fixed NOx of microalgae and the rate of industrial discharge NOx match, and reduce the occupied area of micro algae culturing device to the greatest extent. 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, with this The efficiency of sample, which carries out industrial waste gas denitration, can occupy a large amount of soil, it is therefore necessary to further increase the breeding efficiency of microalgae. Organic carbon source is added to carry out Heterotrophic culture or luminous energy and support to be to accelerate the feasible method of micro algae growth, however adding organic carbon source Afterwards, algae solution causes the growth of bacterium to be significantly faster than the growth of microalgae easily by the pollution of harmful bacteria, supports so as to cause microalgae It grows unsuccessfully.

Large-scale cultivation microalgae needs a large amount of water, if do not recycled to it, can greatly increase cultivation at This.Known most of microalgaes do not adapt to the ammonium salt solution of high concentration, for example sulphur ammonium is used frequently as microalgae in the prior art Inhibitor；And nitrogen source is provided for microalgae with salt made from earth containing a comparatively high percentage of sodium chloride, it may be difficult to recycle to breeding water, reason is that metal ion can be It is constantly accumulated in breeding water body, its salinity is caused to gradually rise, and high salinity usually has apparent inhibition to make the growth of microalgae With.

Summary of the invention

For aforementioned the deficiencies in the prior art, microalgae biomass and industrial waste gas denitration are produced the present invention provides a kind of Integrated processes and system, main contents are as follows.

1. a kind of integrated processes for producing microalgae biomass and industrial waste gas denitration, comprising the following steps:

(1) the step of cultivating microalgae；In the step, the algae solution at the end of making the step by microalgae metabolism is (excellent in alkalinity PH value > 8 are selected, more preferable pH value is 9~11)；

(2) the step of isolating microalgae from the algae solution that step (1) harvests to obtain microalgae and alkaline residue；

(3) from the microalgae that step (2) obtains, fluid composition, protein, carbohydrate, nucleic acid, pigment, dimension are extracted The step of one of raw element, growth factor or any combination thereof, (preferably extracts one of fluid composition, protein, starch, cellulose Or any combination thereof the step of)；

With

(3) 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 (2) obtains, is step with the solution after absorption NOx (1) cultivating microalgae process provides the step of nitrogen source；

(B) it is nitric acid and/or nitrous acid (preferably nitric acid and optional nitrous acid) by the NOx conversion in industrial waste gas, incites somebody to action The alkaline residue that step (2) obtains is mixed with the nitric acid and/or nitrous acid (preferably nitric acid and optional nitrous acid), mixed with this The step of conjunction solution provides nitrogen source for the microalga cultivation process of step (1).

2. the method according to 1, breeding way is Heterotrophic culture and/or luminous energy and supports.

3. the method according to 2, 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, cellulose hydrolysate and cellulose hydrolysate, more preferable glucose.

4. according to method described in 2 or 3, which is characterized in that controlling the concentration of organic carbon source used in 0.1g/L algae Liquid~30g/L algae solution, preferably 1g/L algae solution~30g/L algae solution, more preferably control is in 2g/L algae solution~10g/L algae solution.

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

6. the method according to 1, which is characterized in that when breeding way is photoautotrophy or luminous energy and supports, with containing CO₂'s Gas is as inorganic carbon source.

7. the method according to 6, which is characterized in that described to contain CO₂Gas be industrial waste gas by purified treatment, It or is the industrial waste gas without containing SOx and NOx.

8. according to 1~7 any method, which is characterized in that described to provide nitrogen source for microalgae in step (3) In solution, in terms of nitrogen-atoms, the amount of nitrogenous compound is 0.1~400mmol/L, preferably 10~300mmol/L, further Preferably 20~200mmol/L.

9. according to the method any in 1~8, which is characterized in that the industrial waste gas is the industry without containing SOx Exhaust gas or industrial waste gas Jing Guo desulfurization process.

10. according to the method any in 1~9, which is characterized in that in the cultivating microalgae later period, do not provide or provide less CO₂Or pH adjusting agent, make the algae solution at the end of cultivation in alkalinity by microalgae metabolism alkali metal nutritive salt；The alkali metal battalion Supporting salt is alkali nitrates, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali One of metal hydrogen phosphates or their any combination (preferred as alkali nitrate and/or alkali metal nitrites salts, and it is optional One of alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate or their any combination).

11. according to the method any in 1~10, which is characterized in that in the breeding process of step (1), into algae solution EM bacterium is added.

12. the method according to 11, which is characterized in that the additional amount of EM bacterium is 1 × 10⁶A/algae solution~9 × 10 L⁸A/ L algae solution, preferably 1 × 10⁷A/algae solution~5 × 10 L⁸A/L algae solution.

13. according to 1~12 any method, which is characterized in that the microalgae is green alga or cyanobacteria, preferably bead Algae, scenedesmus, single needle algae or spirulina.

14. according to 1~13 any method, which is characterized in that cultivation temperature is 15~40 DEG C, and algae solution pH value is 6 ~11.

15. a kind of system for producing microalgae biomass and industrial waste gas denitration, the system include:

(1) for one of photoautotrophy unit of cultivating microalgae, luminous energy and feeding unit, Heterotrophic culture unit or they Any combination；

(2) for the algae solution of harvest to be separated into the separative unit of microalgae and alkaline residue；

(3) for extracting fluid composition, protein, carbohydrate, nucleic acid, pigment, vitamin, growth from microalgae One of factor or any combination thereof extraction unit (preferably extraction fluid composition, protein, one of carbohydrate or its The combined extraction unit of meaning)；

(4) the denitration unit of the NOx in industrial waste gas is absorbed with lye, by the NOx conversion in industrial waste gas be nitric acid and/ Or the combination of one or both of denitration unit of nitrous acid；

(5) combination of one or both of following material transportation routes (A), material transportation route (B)；

(A) for mixing and being delivered in (1) with the nitric acid and/or nitrous acid obtained in (4) by the alkaline residue in (2) Cultivate the material transportation route of unit；

(B) it is used to for the alkaline residue in (2) being delivered to the material transportation route of lye denitration unit in (4), and is used for Solution after absorption NOx in the lye denitration unit is delivered to material transportation route of cultivation unit in (1).

16. a kind of method using Ethanol Production by Biomass Fermentation, which is characterized in that raw material is made by 1 method, (excellent It is selected as the carbohydrate as made from 1 method, the more preferably starch as made from 1 method and/or cellulose).

17. a kind of method for producing protein fibre, which is characterized in that protein made from the method that raw material is 1.

18. a kind of method for producing bio-fuel, which is characterized in that fluid composition made from the method that raw material is 1.

19. according to method described in 18, which is characterized in that by being selected from distillation, extracting plus hydrogen, cracking, isomerization, folding Fluid composition is processed into one or more of Fuel Petroleum, diesel fuel and jet fuel by the group technology of conjunction.

20. a kind of system for producing bio-fuel, comprising:

(1) it is selected from the combination of distillation unit, extraction unit, hydrogenation unit, Cracking Unit, isomerization unit, Superposition unit；

System defined in (2) 15；

(3) for the fluid composition obtained in (2) to be delivered to the material transportation route of unit in (1).

The present invention achieves following technical effect.

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.

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

According to the present invention, specific microalgae, such as chlorella, scenedesmus, single needle algae or spirulina, they can be metabolized simultaneously NO^3-And NO^2-, 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.

According to the present invention, when accelerating micro algae growth using organic carbon source (Heterotrophic culture or luminous energy and support), do not need into Row sterilization (without steam sterilizing and does not use fungicide), but by the way that EM bacterium is added in algae solution, it effectively inhibits The breeding of harmful bacteria, to make the present invention with greater advantage.

According to the present invention, after EM bacterium being added in algae solution, microalgae is inorganic nitrogen-sourced with high efficiency consumption, makes the present invention ten Divide and is suitable for industrial waste gas denitration.

Detailed description of the invention

Fig. 1 is photoautotrophic micro algae growth curve.

Fig. 2 is luminous energy and feeding micro algae growth curve.

Fig. 3 is using salt made from earth containing a comparatively high percentage of sodium chloride as the micro algae growth curve of nitrogen source.

Fig. 4, Fig. 5 are the micro algae growth curve for adding a large amount of organic carbon sources.

Fig. 6 is the schematic diagram of NOx absorption technique.

Fig. 7, Fig. 8 are using NOx fixer as the micro algae growth curve of nitrogen source.

Fig. 9 is the micro algae growth curve of addition EM bacterium under conditions of unglazed heterotrophism.

Figure 10 is NOx absorptivity versus time curve.

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 Bright published range, no matter whether separately disclosing these numerical value pair herein.

(1) integrated processes of microalgae biomass and industrial waste gas denitration are produced

With

(3) combination of one or both of following step (A), step (B)；

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 (goes out without steam without disinfecting action Bacterium and be added without fungicide), but be added EM bacterium.

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, cellulose hydrolysate and cellulose hydrolysate, preferably selection are 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 0.1g/L Algae solution~30g/L algae solution is preferably controlled in 1g/L algae solution~30g/L algae solution, and more preferably control is in 2g/L algae solution~10g/L algae Liquid.Organic carbon source can be added at one time, and can also be added several times.

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.

In accordance with the present invention, it was found that there are two types of functions for EM bacterium tool, first is that can promote the growth of microalgae；Second is that can inhibit to microalgae Harmful bacterial reproduction.It should be appreciated that the purpose of the present invention is obtain microalgae biomass, therefore the dosage of EM bacterium should meet plus The needs of fast micro algae growth can not neither work because dosage is very few, and cannot compete and consume with microalgae due to dosage is excessive Excessive nutriment.The adding manner (for example be added at one time or be added several times) and any EM bacterium dosage of any EM bacterium It is 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.

In step (2), preferably relying upon microalgae metabolism makes pH value > 8 of algae solution at the end of cultivating, and is more preferably metabolized by microalgae Make the pH value 9~11 of algae solution at the end of cultivating.

The present inventor is had found by a large number of experiments, for photoautotrophy or luminous energy and feeding breeding way, when microalgae is metabolized Alkali nitrates, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal phosphorus When one of sour hydrogen salt or any combination thereof, if not being passed through CO into algae solution in the breeding process of microalgae₂Or it is added without pH Regulator, then the pH value of algae solution can rise, especially when microalgae metabolism alkali nitrates, alkali metal nitrites salts or combinations thereof 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 nutrition When substance, in order to avoid the pH value of culture solution exceeds the permitted range of micro algae growth, the present invention is preferably at least with containing CO₂Gas Body provides part carbon source for the breeding process of microalgae, contains CO by control₂Gas intake, can be convenient by algae solution PH value controls in suitable range.As described previously for photoautotrophy or luminous energy and feeding breeding way, when the culture of microalgae In liquid containing alkali nitrates, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, When one of alkali metal hydrogen phosphate or any combination thereof, if not providing or providing less CO in the breeding process of microalgae₂(or PH adjusting agent), then the trend risen is presented in the pH value of algae solution.Using this phenomenon, can in the cultivating microalgae later period, do not provide or CO is provided less₂(or pH adjusting agent) makes the algae solution at the end of cultivation in alkalinity, thus can use separation by microalgae metabolism The alkaline residue of microalgae absorbs the NOx in exhaust gas or neutralizes the acid solution after fixed NOx out, and is then mentioned with it for cultivating microalgae For required nitrogen source.

For the breeding way of Heterotrophic culture, can also use and identical hand used by the above-mentioned breeding way later period Section makes the algae solution at the end of cultivating in alkalinity.But illumination according to the present invention, is provided in the heterotrophism cultivating microalgae later period, this can be accelerated One adjusts algae solution in the process of alkalinity.

According to the present invention, various alkali metal nutritive salt above-mentioned are preferably the alkali metal nutritive salt of sodium and/or potassium.

Inventors have found that using isolate the alkaline residue after microalgae can expeditiously absorb NOx in exhaust gas or Acid solution after neutralizing fixed NOx, obtains containing NO₃ ^-And/or NO₂ ^-Solution, which can directly be next group both culturing microalgae Nitrogen source is provided, after the nitrogen source is metabolized by microalgae, can make algae solution in alkalinity again, one mode can be supported in microalgae in this way It grows and realizes closed circulation between culture solution and the absorbing liquid or neutralizer of industrial waste gas denitrification process, thus by " both culturing microalgae " Organically connected with " industrial waste gas denitration ", not only can use microalgae nitrogen pollutant is expeditiously converted to it is useful Biomass, and " both culturing microalgae " and " exhaust gas denitration " is made to become two relatively independent processes, avoid the mutual shadow of the two It rings.

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, for example nitric acid absorption process, the method for the absorbing emulsions NOx formed with water with organic sulfoxide or fixed with nitrifier The method of NOx.

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 higher concentration Nitric acid is the oxidative absorption method of absorbent, is fixed as the oxidative absorption method of absorbent or with nitrifier using hydrogen peroxide and nitric acid The method of NOx.

, 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 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 CO₂It can be improved rapidly by own metabolism when (or pH adjusting agent) The microalgae of algae solution pH value, cultivating these microalgaes can be further improved the efficiency of cultivating microalgae process.Inventor is by a large amount of examinations It tests, filters out the following microalgae that can improve algae solution pH value rapidly, it is above-mentioned micro- such as chlorella, single needle algae, scenedesmus or spirulina The pH value of algae solution can be increased to 9~11 in 1~24 hour by algae, meet algae solution efficiently anti-with nitric acid and/or nitrous acid It should 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 0.1~400mmol/L, preferably 10~300mmol/L, is still more preferably 20~200mmol/L.

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, alkaline residue can be reduced to the absorption efficiency of NOx.As needed, SOx in exhaust gas can also be reduced to by conventionally known technological means and not significantly affect this hair by those skilled in the art The level that bright integrated processes are implemented.The flue gas of general industry discharge, contains a large amount of SOx, therefore right especially in coal-fired flue-gas In 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).

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 or it contains SOx and/or NOx is not enough to influence realization of the invention.It is described to contain CO₂Gas can for by purified treatment (removing exhaust gas In SOx and NOx) industrial waste gas, or be the industrial waste gas without containing SOx and NOx.

(2) system of cultivating microalgae and industrial waste gas denitration

A kind of system producing microalgae biomass and industrial waste gas denitration, the system include:

According to the present invention, the number of any unit in (1) can be one or more；Either open supports Grow, it is enclosed cultivation one of, be also possible to combination.The photoautotrophy unit can be selected from pond, raceway pond, light One of bioreactor or their combination, preferably pond or raceway pond.The luminous energy and feeding unit and Heterotrophic culture list Member is both preferably bioreactor.

According to the present invention, a kind of preferred embodiment is at least one photoautotrophy unit in (1), and also The combination of one or both of the simultaneous feeding unit of luminous energy, Heterotrophic culture unit.The embodiment is used for while carrying out industrial waste gas denitration With emission reduction CO₂。

According to the present invention, another preferred embodiment is, in (1) for luminous energy and feeding unit, Heterotrophic culture unit it One or both combination.The embodiment is mainly used for carrying out industrial waste gas denitration.

According to the present invention, the separative unit in (2) can be any existing for algae solution to be separated into microalgae and feeding algae The separative unit of raffinate, for example algae solution is separated using one of modes such as flocculation, centrifugation, filtering, sedimentation or their combination Unit；It is preferred that separating the unit of algae solution using subsidence style.

According to the present invention, the extraction unit of (3) can use various known those.

According to the present invention, the denitration unit for absorbing the NOx in industrial waste gas in (4) with lye, either only with lye For the denitration unit of absorbent, it is also possible to be to partially absorb the denitration unit of agent with lye, such as with lye/organic sulfoxide cream Liquid is the denitration unit of absorbent.

According to the present invention, it is the denitration unit of nitric acid and/or nitrous acid by the NOx conversion in industrial waste gas in (4), both may be used It to be chemical denitration unit, for example by the denitration unit of absorbent, Yi Shui/organic sulfoxide lotion of nitric acid is the denitration of absorbent Unit, using hydrogen peroxide and nitric acid as the denitration unit of absorbent；It is also possible to biological denitrification unit, for example is converted using nitrifier The denitration unit of fixed NOx.

According to the present invention, the denitration unit in (4) is preferably any to be set to chemical plant installations, especially oil refining apparatus, stone Oily chemical plant installations, coal chemical engineering equipment, biochemical industry device denitration unit.

According to the present invention, (1), (2), the preferred geographical location of whole units in (3) are close, for example, 100 kilometers of radius, Within the scope of 50 kilometers, 10 kilometers or 5 kilometers.

According to the present invention, material transportation route described in (4) can be pipeline, vehicle such as automobile or train, preferably Pipeline.

(3) method of bio-fuel is produced

A method of producing bio-fuel, the fluid composition of the raw material sources of this method step (3) in 1.

According to the method for aforementioned production bio-fuel, by selected from distillation, extracting plus hydrogen, cracking, isomerization, overlapping Fluid composition is processed into one or more of Fuel Petroleum, diesel fuel and jet fuel by group technology.

The fluid composition is mainly made of hydrocarbon and/or grease (fatty glyceride), can be by successive or same When broken wall is carried out to microalgae, extracting obtains.Existing technological means can be used to complete for the broken wall, for example utilize heat, machine One of tool power, alkali, acid, enzyme or their combination carry out broken wall.The extracting can using organic solvent such as hexane into Row extracting, or use CO₂Carry out supercritical extraction.

When the fluid composition contains the substance unfavorable to certain following process, it can use but be not limited to add hydrogen By these devolatilizations, such as hydrogenation deoxidation, hydrodenitrogeneration, hydrodemetallization etc..

The cracking can be thermal cracking, catalytic cracking such as fluid catalytic cracking, be hydrocracked, steam cracking or water Thermal cracking.

Using the mixture of the fluid composition or the fluid composition and petroleum hydrocarbon as raw material, can be obtained by steam cracking Obtain the alpha-olefin of low-carbon alkene or more Long carbon chain.Such as use tube cracking furnace, cracking heater outlet temperature be 760~860 DEG C, Under conditions of the mass ratio of dilution steam generation and cracking stock is 0.10~0.50, the low-carbon alkene of C2~C4 can be produced；It is cracking Heater outlet temperature be 560~680 DEG C under conditions of, can produce the mixing alpha-olefin of C6~C24, the especially C6 of high value~ The alpha-olefin of C12.

Using catalytic cracking, low-carbon alkene, such as propylene can be equally obtained.

Fatty glyceride can be converted to fatty acid methyl ester using transesterification technique (transesterification). According to the actual needs setting distillation unit may be selected, to be fitted in the fatty acid methyl ester that usual biodiesel is C14~C18 Suitable fraction is used as biodiesel.According to actual needs, it may be selected to improve the steady of biodiesel using the means such as hydrogen or blending are added It is qualitative.The biodiesel both can be used alone, and can also be used in mixed way with common diesel.

Diesel fuel can also be obtained by carrying out deoxidation to the fluid composition and adding the combined treatment process of hydrogen, than If elder generation carries out deoxidation treatment to the fluid composition in the presence of high temperature and hydrogen, then again by adding hydrogen to be saturated double bond.

By F- T synthesis, the fuel of ultra-low sulfur, such as Fuel Petroleum, diesel fuel, jet fuel can be obtained Deng.

By the combination of above-mentioned technique, objectionable impurities in fluid composition can be removed, obtain lighter hydrocarbons, to the lighter hydrocarbons into one Step cracking, isomerization or overlapping can be obtained Fuel Petroleum.

(4) system of bio-fuel is produced

A kind of system producing bio-fuel, comprising:

System defined in (2) 15；

According to the present invention, (1), the preferred geographical location of whole units in (2) are close, such as in 100 kilometers of radius, 50 public In, within the scope of 10 kilometers or 5 kilometers.

According to the present invention, material transportation route described in (3) can be pipeline, vehicle such as automobile or train, preferably Pipeline.

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 discharge_xAs 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.

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 NO₃Content 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 4.

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

3 Heterotrophic culture base of table

4 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.

Embodiment 1

The present embodiment is for illustrating " addition EM bacterium is on the photoautotrophic influence of microalgae ".

It (is come from using BG11 culture medium (adding nutritional ingredient by table 1, culture solution is without sterilization treatment) culture chlorella Sinopec microalgae algae library, number Chlorella sp.RIPP-1), between 20~30 DEG C, it is empty to be passed through compression Gas and CO₂Culture, is passed through CO as algae solution PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.Nature is used in incubation Day optical culture, daylight intensity reach as high as 60000 luxs, detect the OD of algae solution daily₆₈₀Value, after continuous culture 14 days Harvest, culture terminate to stop within first 1 day being passed through containing CO₂Gaseous mixture, terminate cultivation after, by being centrifugally separating to obtain algal gel and feeding algae Raffinate.The growth curve of microalgae is shown in Fig. 1, and the difference of two in Fig. 1 test is only that: EM bacterium is not added in one of test, Another test presses 3.6 × 10⁶The additive amount of a/L algae solution adds EM bacterium.For adding the test of EM bacterium, supervised in breeding process Survey count of bacteria < 6.7 × 10 of algae solution⁶A/mL algae solution, algae solution pH is increased to 9.8 naturally at the end of measuring cultivation.From Fig. 1 As it can be seen that addition EM bacterium promotes the growth of microalgae under the conditions of photoautotrophy.

Embodiment 2~5 for illustrate " luminous energy and support in, influence of the EM bacterium additive amount to microdisk electrode ".

Embodiment 2

It (is come from using BG11 culture medium (adding nutritional ingredient by table 1, culture solution is without sterilization treatment) culture chlorella Sinopec microalgae algae library, number Chlorella sp.RIPP-1), the glucose of 2g/L is added in incubation, controls temperature Between 20~30 DEG C, it is passed through compressed air and CO₂Culture, is passed through CO as algae solution PH > 10₂, stop as algae solution PH < 7.5 logical Enter CO₂.Natural daylight culture is used in incubation, daylight intensity reaches as high as 60000 luxs, detects algae solution daily OD₆₈₀Value, the growth curve of microalgae are shown in Fig. 2.Wherein EM additive amount is 3.6 × 10⁶A/L algae solution monitors algae in breeding process Count of bacteria < 8 × 10 of liquid⁶A/mL algae solution, continuous culture harvest after 14 days, and culture terminates to stop within first 1 day being passed through CO₂Flue gas, And algae solution pH is made to be increased to 9.4 naturally, then terminate to cultivate, is centrifugally separating to obtain algal gel and feeding algae raffinate.

Embodiment 3

The present embodiment and the difference of embodiment 2 are only that: EM additive amount is 1.8 × 10⁷A/L algae solution.It is supervised in breeding process Survey count of bacteria < 1 × 10 of algae solution⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 9.3 naturally.The life of microalgae Long curve is shown in Fig. 2.

Embodiment 4

The present embodiment and the difference of embodiment 2 are only that: EM additive amount is 3.6 × 10⁷A/L algae solution.It is supervised in breeding process Survey count of bacteria < 2 × 10 of algae solution⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 8.9 naturally.The life of microalgae Long curve is shown in Fig. 2.

Embodiment 5

The present embodiment and the difference of embodiment 2 are only that: EM additive amount is 7.2 × 10⁷A/L algae solution.It is supervised in breeding process Survey count of bacteria < 5.8 × 10 of algae solution⁷A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 8.7 naturally.Microalgae Growth curve is shown in Fig. 2.

Comparative example 1

The difference of this comparative example and embodiment 2 is only that: not adding EM bacterium.The count of bacteria of algae solution is monitored in breeding process It has been up to 1.2 × 10⁸A/mL algae solution, the pH for measuring algae solution at the end of cultivating are increased to 7.9 naturally.The growth of microalgae is bent Line is shown in Fig. 2.

It can be seen in fig. 2 that addition EM bacterium promotes the growth of microalgae under the conditions of luminous energy is simultaneous feeding.

Embodiment 6~8 is for illustrating " metabolism of the microalgae to NO3-N and NO2-N ".

Embodiment 6

It (is come from using BG11 culture medium (adding nutritional ingredient by table 1, culture solution is without sterilization treatment) culture chlorella Sinopec microalgae algae library, number Chlorella sp.RIPP-1), between 20~30 DEG C, it is empty to be passed through compression Gas and CO₂Culture, is passed through CO as algae solution PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.Nature is used in incubation Day optical culture, daylight intensity reach as high as 60000 luxs, detect the OD of algae solution daily₆₈₀Value, continuous culture 14 days.It is micro- The growth curve of algae is shown in Fig. 3.

Embodiment 7

The present embodiment and the difference of embodiment 6 are only that: the sodium nitrate of 1.5g/L in culture medium is substituted for 1.35g nitrous Sour sodium and 0.15g sodium nitrate.The growth curve of microalgae is shown in Fig. 3.

Embodiment 8

The present embodiment and the difference of embodiment 7 are only that: culture microalgae is that single needle algae (comes from Sinopec microalgae algae Library, number Monoraphidium dybowskii.RIPP-50).The growth curve of microalgae is shown in Fig. 3.

It can be seen from figure 3 that using the microalgae algae of institute's breeding, it can be preferably raw using NO3-N and NO2-N simultaneously It is long.

Embodiment 9~16 is for illustrating that " in the case where largely addition organic carbon source, EM bacterium is metabolized microalgae inorganic nitrogen-sourced Influence ".

Embodiment 9

First using BG11 culture medium (adding nutritional ingredient by table 1, culture solution is without sterilization treatment) culture chlorella (coming from Sinopec microalgae algae library, number Chlorella sp.RIPP-1)；Work as OD₆₈₀When value is 4, mended 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 solution CO is passed through when PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.Natural daylight culture is used in incubation, daylight is strong Degree 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, daily Detect the OD of 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, monitoring the count of bacteria of algae solution in breeding process is up to 9.7 × 10⁶ A/mL algae solution, continuous culture harvest after 8 days, and last time stops being passed through CO after glucose is added₂, terminate algae solution PH when cultivation Value is 8.6, is centrifugally separating to obtain algal gel and feeding algae raffinate.Analyze the NO supported in algae raffinate₃With NO₂Total content < 10 μ g/g. The growth curve of microalgae is shown in Fig. 4.

Embodiment 10

The present embodiment and the difference of embodiment 9 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 raffinate₃With NO₂Total content < 200 μ g/g.The growth curve of microalgae is shown in Fig. 4.

Embodiment 11

The difference of the present embodiment and embodiment 9 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 analyzed₃With NO₂Total 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 11 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 raffinate₃With NO₂Total content < 200 μ g/g.The growth curve of microalgae is shown in Fig. 4.

Comparative example 2

The difference of this comparative example and embodiment 9 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 4。

As can be seen from Fig. 4, addition EM bacterium is greatly facilitated the growth of microalgae and consumes rapidly inorganic nitrogen-sourced.

Embodiment 13

First using BG11 culture medium (adding nutritional ingredient by table 1, culture solution is without sterilization treatment) culture chlorella； Work as OD₆₈₀When value is 4, a Heterotrophic culture base nutritional ingredient is added by 3 specified amount of table.Between 20~30 DEG C, lead to Enter compressed air and CO₂Culture, is passed through CO as algae solution PH > 10₂, stop being passed through CO as algae solution PH < 7.5₂.In incubation Using natural daylight culture, daylight intensity reaches as high as 60000 luxs, first in illumination autotrophy item after chlorella inoculation It is cultivated under part 2 days, then adds the glucose of 2g/L, and press 1.8 × 10⁸The amount of a/L algae solution adds EM bacterium, detects algae daily The OD of liquid₆₈₀Value；The glucose of 10g/L is added in culture again after 3 days, and presses 1.8 × 10⁸A/L algae solution adds EM bacterium；Culture 2 Glucose 10g/L is added after it again, monitoring the count of bacteria of algae solution in breeding process is up to 2.9 × 10⁷A/mL algae solution, Continuous culture harvests after 14 days, and last time stops being passed through CO after glucose is added₂, terminating algae solution pH value when cultivation is 9.2, from The isolated algal gel of the heart and feeding algae raffinate.Analyze the NO supported in algae raffinate₃With NO₂Total content < 10 μ g/g.The growth of microalgae Curve is shown in Fig. 5.

Embodiment 14

The difference of the present embodiment and embodiment 13 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 raffinate₃With NO₂Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 5.

Embodiment 15

The present embodiment and the difference of embodiment 13 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 NO₃With NO₂Total content < 10 μ g/g.The growth curve of microalgae is shown in figure 5。

Embodiment 16

The present embodiment and the difference of embodiment 14 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 the NO supported in algae raffinate₃With NO₂Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 5.

As can be seen from Fig. 5, using potassium nitrate or sodium nitrate as nitrogen source, the growth that EM bacterium promotes microalgae is added.

Embodiment 17~18 be used for illustrate " using support algae obtain alkaline residue absorb NOx and with absorption NOx after solution The case where continuing cultivating microalgae ".

Embodiment 17

Using O₃Auxiliary law absorbs NOx.

Using NO₂Practical flue gas is simulated with the gaseous mixture of NO, using compressed air as carrier gas, NOx flow is 0.3L/min, is contained O₃The mobile ozone generator of XM-Y type that produces from Qingdao Xin Mei cleaning equipment Co., Ltd of gas, flow 1L/min, Make total flow up to 150L/h after mixing air, measures the NOx concentration of entrance and exit gas, NOx absorptivity is calculated as follows；

NOx absorptivity=(1- exit NOx concentration/inlet NOx concentration) × 100%；

Wherein the total concentration of entrance NOx is basically stable at 620mg/m³(wherein NO content is about 600mg/m³, NO₂Content is about For 20mg/m³)

Flow chart is shown in Fig. 6, wherein absorption tower diameter 100mm, high 700mm, and tower bottom is equipped with sieve-mesh gas distributor, In hold 3L embodiment 16 generation feeding algae raffinate.NOx mixed gas is passed directly into absorption tower when operation, 22h is absorbed and stops Feeding algae raffinate in washing tower (for removing CO2) is taken out, measures NO therein by operation₃With NO₂Total content be 5900 μ g/g.

Utilize NOx absorbing liquid cultivating microalgae.

Using above-mentioned NOx absorbing liquid as micro algae culturing liquid, other nutriments in addition to nitrogen source are provided by BG11 culture medium, Cultivate chlorella, with embodiment 16, monitoring the count of bacteria of algae solution in breeding process is up to 1.8 for the rest part of cultural method ×10⁷A/mL algae solution, continuous culture harvest after 14 days, and last time stops being passed through CO after glucose is added₂, terminate algae when cultivation Liquid pH value is 9.1, is centrifugally separating to obtain algal gel and feeding algae raffinate.Analyze the NO supported in algae raffinate₃With NO₂Total content < 10 μ G/g can promote the growth of microalgae, again from figure 7, it is seen that using NOx absorbing liquid to cultivate nutrient solution after addition EM bacterium By the NO in algae solution₃And NO₂It sponges, and is restored to alkalinity, absorbed so as to be further used as the alkalinity of exhaust gas denitration Liquid.

Embodiment 18

NOx is absorbed as described in Example 17, the difference is that only: being held the 3L that embodiment 10 obtains in absorption tower and is supported Algae raffinate.After absorbing 22h, the feeding algae raffinate in washing tower (for removing CO2) is taken out, NO therein is measured₃With NO₂Total content be 5800 μ g/ g。

Utilize NOx absorbing liquid cultivating microalgae.

Using above-mentioned NOx absorbing liquid as micro algae culturing liquid, other nutriments in addition to nitrogen source are provided by BG11 culture medium, Cultivate single needle algae, with embodiment 10, monitoring the count of bacteria of algae solution in breeding process is up to 9.2 for the rest part of cultural method ×10⁶A/mL algae solution, continuous culture harvest after 8 days, and last time stops being passed through CO after glucose is added₂Flue gas terminates cultivation When algae solution pH value be 8.7, be centrifugally separating to obtain algal gel and feeding algae raffinate.Analyze the NO supported in algae raffinate₃With NO₂Total content < 200 μ g/g use NOx absorbing liquid to cultivate nutrient solution, can promote the growth of microalgae after addition EM bacterium as can be seen from Fig. 8, then Once by the NO in algae solution₃And NO₂It sponges, and is restored to alkalinity, absorbed so as to be further used as the alkalinity of denitration Liquid.

Embodiment 19 is for illustrating " EM bacterium is on microalgae without photoheterotrophic influence ".

Embodiment 19

The present embodiment and the difference of embodiment 9 are only that: being cultivated under no light condition.Measure the pH of algae solution when terminating cultivation Value is 7.7.The growth curve of microalgae is shown in Fig. 9.

Comparative example 3

This comparative example is for illustrating " absorption and assimilation situation of the EM bacterium to NOx ".

The difference of this comparative example and embodiment 9 is only that following aspect: simple culture EM bacterium；Culture solution is carried out before culture Sterilization treatment；Culture medium still uses BG11 (table 1), but NO₃ ^-Initial concentration be 6900ug/g；Culture 14 days.Analysis culture knot NO when beam₃ ^-And NO₂ ^-Total content is 5600ug/g.As it can be seen that EM bacterium is far low to inorganic nitrogen-sourced wear rate during the growth process In microalgae.

Embodiment 20

The present embodiment absorbs NOx with the feeding algae raffinate of alkalinity for illustrating.

The alkalinity of Example 14 supports algae raffinate 3L；Analyze the alkalinity support algae raffinate in potassium, Na ion concentration, prepare with Its aqueous solution 3L with identical potassium concentration and Na ion concentration, pairing anion are HCO₃ ^-And CO₃ ^2-, prepared water Solution ph is 9.27, and the pH value for supporting algae raffinate with the alkalinity of embodiment 14 is essentially identical.It is residual that algae is supported with above-mentioned alkalinity respectively Liquid and the aqueous solution of preparation are absorbing liquid, absorb NOx using the method for embodiment 17, see Figure 10 to the absorption efficiency curve of NOx.

As seen from Figure 10, the lye that algae raffinate is apparently higher than preparation to the absorptivity of NOx is supported.

Claims

(1) the step of cultivating microalgae；In the step, the algae solution at the end of making the step by microalgae metabolism is in alkalinity；Cultivation side When formula is photoautotrophy or luminous energy and supports, with containing CO₂Gas as inorganic carbon source；

(3) from the microalgae that step (2) obtains, extract fluid composition, protein, carbohydrate, nucleic acid, pigment, vitamin, The step of one of growth factor or any combination thereof；

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 (2) obtains, is step (1) with the solution after absorption NOx Cultivating microalgae process provide nitrogen source the step of；

It (B) is nitric acid and/or nitrous acid, the alkaline residue that step (2) is obtained and the nitre by the NOx conversion in industrial waste gas The step of acid and/or nitrous acid mix, provide nitrogen source with the mixed solution for the microalga cultivation process of step (1).

2. according to the method described in claim 1, the breeding way in (1) is Heterotrophic culture and/or luminous energy and supports.

3. according to the method described in claim 2, it is characterized in that, used organic carbon source is selected from sugar, organic acid, organic acid At least one of salt, alcohol, cellulose hydrolysate and glucidtemns.

4. according to the method in claim 2 or 3, which is characterized in that controlling the concentration of organic carbon source used in 0.1g/ L algae solution~30g/L algae solution.

5. the method according to claim 1, wherein when breeding way is photoautotrophy or luminous energy and supports, light intensity For 1000~200000 luxs.

6. the method according to claim 1, wherein described contain CO₂Gas be Industry Waste by purified treatment Gas, or be the industrial waste gas without containing SOx and NOx.

7. described to provide the solution of nitrogen source for microalgae the method according to claim 1, wherein in step (4) In, in terms of nitrogen-atoms, the amount of nitrogenous compound is 0.1~400mmol/L.

8. the method according to claim 1, wherein the industrial waste gas is the industrial waste gas without containing SOx Or the industrial waste gas Jing Guo desulfurization process.

9. the method according to claim 1, wherein not providing or providing less CO in the cultivating microalgae later period₂Or pH Regulator makes 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 their combination.

10. the method according to claim 1, wherein EM is added into algae solution in the breeding process of step (1) Bacterium.

11. according to the method described in claim 10, it is characterized in that, the additional amount of EM bacterium is 1 × 10⁶A/algae solution~9 L × 10⁸A/L algae solution.

12. according to the method for claim 11, which is characterized in that the additional amount of EM bacterium is 1 × 10⁷A/algae solution~5 L × 10⁸A/L algae solution.

13. the method according to claim 1, wherein the microalgae is green alga or cyanobacteria.

14. algae solution pH value is 6~11 the method according to claim 1, wherein cultivation temperature is 15~40 DEG C.

(1) for one of photoautotrophy unit of cultivating microalgae, luminous energy and feeding unit, Heterotrophic culture unit or theirs is any Combination；

(3) for extracting fluid composition, protein, carbohydrate, nucleic acid, pigment, vitamin, growth factor from microalgae One of or any combination thereof extraction unit；

(4) the denitration unit of the NOx in industrial waste gas is absorbed with (2) neutral and alkali raffinate, is nitre by the NOx conversion in industrial waste gas The combination of one or both of the denitration unit of acid and/or nitrous acid；

(A) for being mixed the alkaline residue in (2) with the nitric acid and/or nitrous acid obtained in (4) and being delivered to cultivation in (1) The material transportation route of unit；

(B) it is used to for the alkaline residue in (2) being delivered to the material transportation route of (4) neutral and alkali raffinate denitration unit, and is used for Solution after absorption NOx in the alkaline residue denitration unit is delivered to material transportation route of cultivation unit in (1).

16. a kind of method using Ethanol Production by Biomass Fermentation, which is characterized in that the first step, by appointing in claim 1~14 Starch and/or cellulose is made in one method；Second step produces ethyl alcohol using the starch and/or the cellulose fermentation.

17. a kind of method for producing protein fibre, which is characterized in that the first step, by method any in claim 1~14 Protein is made；Second step utilizes the protein production protein fibre.

18. a kind of method for producing bio-fuel, which is characterized in that the first step, by method system any in claim 1~14 Obtain fluid composition；Second step, by selected from distillation, extracting, plus hydrogen, cracking, isomerization, overlapping group technology, by the oil group It closes object and is processed into one or more of Fuel Petroleum, diesel fuel and jet fuel.

19. a kind of system for producing bio-fuel, comprising:

(2) system defined in claim 15；