CN105985909A - Combined method and system for producing microalgae biomass and denitrating industrial waste gas - Google Patents

Combined method and system for producing microalgae biomass and denitrating industrial waste gas Download PDF

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Publication number
CN105985909A
CN105985909A CN201510046935.8A CN201510046935A CN105985909A CN 105985909 A CN105985909 A CN 105985909A CN 201510046935 A CN201510046935 A CN 201510046935A CN 105985909 A CN105985909 A CN 105985909A
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microalgae
algae
waste gas
unit
algae solution
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CN105985909B (en
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荣峻峰
朱俊英
纪洪波
周旭华
黄绪耕
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/59Biological synthesis; Biological purification

Abstract

The invention relates to a combined method and a system for producing microalgae biomass and denitrating industrial waste gas. The method includes the steps of: 1) breeding microalgae; 2) separating the microalgae from microalgae liquid to obtain the microalgae and an alkaline residual liquid; 3) extracting the biomass from the microalgae; and 4) converting NOx in the industrial waste gas into nitrates with the alkaline residual liquid, wherein the nitrates serve as a nitrogen source in the microalgae breeding process. In the invention, a cyclic economic mode is established for reducing emission of industrial waste gas pollutants and producing the microalgae biomass.

Description

A kind of integrated processes producing microalgae biomass and industrial waste gas denitration and system
Technical field
The present invention relates to a kind of integrated processes producing microalgae biomass and industrial waste gas denitration and system.
Background technology
Energy and environment are the important topics that human social is faced.On the one hand, support The fossil energy of mankind's modern civilization is non-renewable, and exploitation alternative energy source is extremely urgent;On the other hand, Produced waste gas and sewage when utilizing fossil energy, caused serious impact to environment, this A little problems need the solution made overall plans and coordinate.
Microalgae is of a great variety and the wide aquatic rudimentary plant of distributed pole, and they are by efficient light cooperation With, convert light energy into the chemical energy of the carbohydrate such as fat or starch, be described as " sunlight driving Activation factory ".Utilize microalgae to produce bioenergy and chemicals is expected to reach " to substitute fossil simultaneously The energy, purify waste gas and sewage " dual purpose.
Nitrogen oxides (NOx) in industrial waste gas is one of main atmosphere pollution, and it not only can produce Third contact of a total solar or lunar eclipse chemical fumes and acid rain, also result in serious greenhouse effect, is the main inducing of atmospheric haze, Therefore the denitration problem of industrial waste gas is increasingly subject to the attention of people.Catalytic reduction method (SCR) is urged with non- Changing reducing process (SNCR) is the most conventional exhaust gas denitration method, and NOx is all reduced into by both approaches The nitrogen of low value, is not reaching to the purpose of recycling NOx.The technological process of alkali absorption method and Equipment is relatively easy, and NOx conversion can become useful nitrite and/or nitrate, but should There is following deficiency in method: concentration of lye can not be the highest, otherwise knot can occurs during absorbing NOx Crystalline substance, causes the blocking on absorption tower, and under low alkaline concentration, will necessarily increase the energy consumption extracting salt made from earth containing a comparatively high percentage of sodium chloride. Nitric acid absorption process is the exhaust gas denitration method of another kind of commercial Application, and the method aqueous solution of nitric acid is inhaled Receive NOx, it is possible to obtain more nitric acid.Nitric acid absorption process is more suitable for nitric acid manufacturing enterprise, for other For enterprise, the storage of nitric acid and the economy existing problems of absorption technique.
Nitrogen is one of nutrient of consuming the soonest during micro algae growth, the most easily lacking.A large amount of consumption Nitrogenous fertilizer be expensive for cultivating microalgae, if cultivating microalgae can be combined with industrial waste gas denitration Get up, on the one hand NOx can be utilized to provide nitrogenous fertilizer for micro algae growth, thus reduce the cost of cultivating microalgae; On the other hand can purify again waste gas, the discharge of minimizing NOx, produce more overall situation benefit.Existing Document discloses " industrial waste gas is passed directly into both culturing microalgae device and carries out method of denitration ", but these All there is following insoluble problem in method: 1. utilizing microalgae to carry out industrial waste gas denitration must solve Limiting its more business-like problems, such as cultivating microalgae needs illumination and warm weather conditions, and Changes in weather necessarily causes the change of microalgae denitration efficiency, and " being passed directly into industrial waste gas " will be difficult to Join waste gas discharge operating mode and both culturing microalgae operating mode, cause two-stage process to interact, it is impossible to meet reality The reduction of discharging requirement produced;2. nitric oxide (NO) is the main component of NOx, and the dissolubility that NO is in water Extremely low, therefore " it is passed directly into industrial waste gas " and cannot solve a large amount of NO in NOx water insoluble and be difficult to inhale The problem received.
In nature, there is the ecological relationship of complexity between microalgae and antibacterial, for specific microalgae And antibacterial, may mutually promote, it is also possible to mutually suppress.Difficulty known to of cultivating microalgae is, There is substantial amounts of noxious bacteria in water and air, these noxious bacteria are unfavorable for the growth of microalgae, seriously Time can cause cultivating unsuccessfully.When using open system cultivating microalgae, it is impossible to realize aseptic condition, quilt The risk of germ contamination is higher;Use the cultivation system closed and carry out strict sterilizing and can realize aseptic State, but for large-scale farming microalgae, the cost of this method is prohibitively expensive.
Produced by chemical engineering industry, amount of NOx is huge, if fix the NOx in industrial waste gas with microalgae, The speed of the speed and industrial discharge NOx that are accomplished by making microalgae fix NOx matches, and reduces micro-as far as possible The floor space of algae culturing device.Generally, photoautotrophic efficiency is less than 30g.m-2.d-1, outdoor big rule The efficiency that mould is cultivated is generally below 10g.m-2.d-1, carrying out industrial waste gas denitration with such efficiency can take Substantial amounts of soil, it is therefore necessary to improve the cultivation efficiency of microalgae further.Add organic carbon source to carry out Heterotrophic culture or luminous energy are held concurrently and are supported the feasible method being to accelerate micro algae growth, but after adding organic carbon source, Algae solution is easily polluted by noxious bacteria, causes the growth of antibacterial to be significantly faster than the growth of microalgae, from And cause both culturing microalgae failure.
Large-scale cultivation microalgae needs substantial amounts of water, if it not being circulated utilization, then and can be significantly Increase aquaculture cost.Known most of microalgae does not adapt to the ammonium salt solution of high concentration, and such as sulfur ammonium exists Prior art is used frequently as the inhibitor of microalgae;And provide nitrogen source with salt made from earth containing a comparatively high percentage of sodium chloride for microalgae, it may be difficult to Recycling breeding water, reason is that metal ion constantly can be accumulated in breeding water body, causes Its salinity gradually rises, and the generally growth to microalgae of high salinity has obvious inhibitory action.
Summary of the invention
For aforementioned the deficiencies in the prior art, the invention provides a kind of microalgae biomass that produces with industrial The integrated processes of exhaust gas denitration and system, its main contents are as follows.
1. produce microalgae biomass and an integrated processes for industrial waste gas denitration, comprise the following steps:
(1) step of cultivating microalgae;In this step, at the end of relying on microalgae metabolism to make this step Algae solution is in alkalescence (preferable ph > 8, more preferably pH value is 9~11);
(2) from the algae solution that step (1) is gathered in the crops, microalgae is isolated to obtain microalgae and alkaline residue Step;
(3) from the microalgae that step (2) obtains, fluid composition, protein, carbon hydrate are extracted The step of one of thing, nucleic acid, pigment, vitamin, somatomedin or its combination in any (preferably carries Take the step of one of fluid composition, protein, starch, cellulose or its combination in any);
With
(3) combination of one or both of following step (A), step (B);
(A) alkaline residue obtained by step (2) absorbs the NOx in industrial waste gas, with absorbing NOx After the cultivating microalgae process that solution is step (1) provide nitrogen source step;
(B) it is nitric acid and/or nitrous acid (preferably nitric acid and optional by the NOx conversion in industrial waste gas Nitrous acid), alkaline residue step (2) obtained and described nitric acid and/or nitrous acid are (preferably Nitric acid and optional nitrous acid) mixing, with the microalga cultivation process that this mixed solution is step (1) The step in nitrogen source is provided.
2., according to the method described in 1, breeding way is that Heterotrophic culture and/or luminous energy are held concurrently and supported.
3. according to the method described in 2, it is characterised in that the organic carbon source used is selected from sugared, organic Acid, acylate, alcohol, cellulose hydrolysate and with at least one in glucidtemns;Preferably Portugal Grape sugar, fructose, acetic acid, sodium acetate, lactic acid, ethanol, methanol, cellulose hydrolysate and cellulose At least one in hydrolysate, more preferably glucose.
4. according to the method described in 2 or 3, it is characterised in that by the concentration control of organic carbon source used System, in 0.1g/L algae solution~30g/L algae solution, preferably 1g/L algae solution~30g/L algae solution, is more preferably controlled System is in 2g/L algae solution~10g/L algae solution.
5., according to the method described in 1, it is characterised in that in step (1), breeding way is luminous energy Autotrophy or luminous energy are held concurrently when supporting, and light intensity is 1000~200000 luxs.
6. according to the method described in 1, it is characterised in that breeding way is that auto-trophy or luminous energy are held concurrently and supported Time, with containing CO2Gas as inorganic carbon source.
7. according to the method described in 6, it is characterised in that described containing CO2Gas be at purification The industrial waste gas of reason, or be the industrial waste gas not containing SOx and NOx.
8. according to the arbitrary described method in 1~7, it is characterised in that in step (3), described For microalgae provide nitrogen source solution in, in terms of nitrogen-atoms, the amount of nitrogen-containing compound be 0.1~ 400mmol/L, preferably 10~300mmol/L, the most preferably 20~200mmol/L.
9. according to described method arbitrary in 1~8, it is characterised in that described industrial waste gas is not Industrial waste gas containing SOx or the industrial waste gas processed through desulfurization.
10. according to described method arbitrary in 1~9, it is characterised in that in the cultivating microalgae later stage, no There is provided or CO is provided less2Or pH adjusting agent, at the end of relying on microalgae metabolism alkali metal nutritive salt to make cultivation Algae solution be alkalescence;Described alkali metal nutritive salt be alkali nitrates, alkali metal nitrites salts, One of alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate or Their combination in any (preferred as alkali nitrate and/or alkali metal nitrites salts, and optional alkali One of metal carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate or it Combination in any).
11. according to described method arbitrary in 1~10, it is characterised in that the cultivation of step (1) Cheng Zhong, adds EM bacterium in algae solution.
12. according to the method described in 11, it is characterised in that the addition of EM bacterium is 1 × 106Individual/L Algae solution~9 × 108Individual/L algae solution, preferably 1 × 107Individual/L algae solution~5 × 108Individual/L algae solution.
13. according to the arbitrary described method in 1~12, it is characterised in that described microalgae be chlorella or Cyanophyceae, preferably chlorella, scenedesmus, single needle algae or spirulina.
14. according to the arbitrary described method in 1~13, it is characterised in that cultivation temperature is 15~40 DEG C, Algae solution pH value is 6~11.
15. 1 kinds of systems producing microalgae biomass and industrial waste gas denitration, this system includes:
(1) hold concurrently support unit, Heterotrophic culture unit for the auto-trophy unit of cultivating microalgae, luminous energy One of or their combination in any;
(2) for the algae solution of results being separated into the separative element of microalgae and alkaline residue;
(3) for from microalgae, extract fluid composition, protein, carbohydrate, nucleic acid, The extraction unit of one of pigment, vitamin, somatomedin or its combination in any (preferably extracts line of oils One of compound, protein, carbohydrate or the extraction unit of its combination in any);
(4) with the denitration unit of the NOx in alkali liquor absorption industrial waste gas, by the NOx in industrial waste gas The combination of one or both of the denitration unit being converted into nitric acid and/or nitrous acid;
(5) one or both of following material transport way (A), material transport way (B) Combination;
(A) for the alkaline residue in (2) is mixed with nitric acid and/or the nitrous acid of acquisition in (4) Merge and be delivered to the material transport way of cultivation unit in (1);
(B) for the alkaline residue in (2) being delivered to the material of alkali liquor denitration unit in (4) Transport way, and it is delivered to (1) for described alkali liquor denitration unit absorbing the solution after NOx The material transport way of middle cultivation unit.
16. 1 kinds of methods utilizing Ethanol Production by Biomass Fermentation, it is characterised in that raw material is by 1 Method prepares, and (carbohydrate preferably prepared by the method for 1, is more preferably by the method for 1 The starch prepared and/or cellulose).
17. 1 kinds of methods producing protein fibre, it is characterised in that raw material be 1 method prepare Protein.
18. 1 kinds of methods producing bio-fuel, it is characterised in that raw material be 1 method prepare Fluid composition.
19. according to the method described in 18, it is characterised in that by selected from distilling, extract, be hydrogenated with, Cracking, isomerization, the group technology of overlapping, be processed into Fuel Petroleum, diesel fuel by fluid composition With one or more in jet fuel.
20. produce a system for bio-fuel, including:
(1) selected from distillation unit, extraction unit, hydrogenation unit, Cracking Unit, isomerization unit, The combination of Superposition unit;
System defined in (2) 15;
(3) for the fluid composition obtained in (2) being delivered to the material conveying of unit in (1) Approach.
The present invention achieves following technique effect.
According to the present invention, support alkalescence produced by algae and support algae residual liquid to the NOx absorption effect in industrial waste gas Rate is higher.
According to the present invention, both culturing microalgae and industrial waste gas denitration are two relatively independent processes, it is to avoid That causes because waste gas discharge is from both culturing microalgae operating mode different influence each other, it is to avoid a large amount of NO are not Being dissolved in water and be difficult to the problem absorbed, the two process relies on the alkaline residue of microalgae to contact Come, it is not necessary to extra alkaline absorption solution or alkalescence neutralizer just can utilize the NOx in industrial waste gas to be Microalgae provides nitrogen source, and this makes the method aquaculture cost of the present invention lower.
Present invention, avoiding the accumulation problem of metal ion, make breeding water body be recycled.
According to the present invention, specific microalgae, such as chlorella, scenedesmus, single needle algae or spirulina, it Can simultaneously metabolism NO3-And NO2-, the environment of high nitrogen concentration can be tolerated, moreover it is possible to by the generation of self Thank and improve rapidly the pH value of algae solution in the cultivation later stage, cultivate these microalgae and can improve conversion further The efficiency of NOx.
According to the present invention, simplify the processing step of industrial waste gas denitration, improve its technical process Economy, such as, for alkali absorption method, it is not necessary to extra alkaline absorption solution and salt made from earth containing a comparatively high percentage of sodium chloride extract step Suddenly;For the method that NOx is fixed as acid, it is not necessary to large-scale storage sour container, without the need for volume Nitric acid/nitrous acid can be changed into the salt made from earth containing a comparatively high percentage of sodium chloride of higher value by outer alkaline neutralizer, for cultivating microalgae Used.
According to the present invention, when using organic carbon source to accelerate micro algae growth, (Heterotrophic culture or luminous energy are held concurrently Support), it is not necessary to the sterilizing that carries out disinfection (does not carry out steam sterilization and does not use antibacterial), but logical Cross addition EM bacterium in algae solution, restrained effectively the breeding of noxious bacteria, so that present invention tool There is bigger advantage.
According to the present invention, after adding EM bacterium in algae solution, microalgae consumes inorganic nitrogen with high efficiency Source, makes the present invention be quite suitable for industrial waste gas denitration.
Accompanying drawing explanation
Fig. 1 is photoautotrophic micro algae growth curve.
Fig. 2 is the micro algae growth curve that luminous energy is held concurrently foster.
The micro algae growth curve that Fig. 3 is is nitrogen source with salt made from earth containing a comparatively high percentage of sodium chloride.
Fig. 4, Fig. 5 are the micro algae growth curve adding a large amount of organic carbon sources.
Fig. 6 is the schematic diagram of NOx absorption technique.
The micro algae growth curve that Fig. 7, Fig. 8 are is nitrogen source with NOx fixative.
Under conditions of Fig. 9 is unglazed heterotrophism, add the micro algae growth curve of EM bacterium.
Figure 10 is NOx absorbance versus time curve.
Detailed description of the invention
The detailed description of the invention of the present invention described further below, it should be noted however that the present invention Protection domain is the most limited to these specific embodiments, but is determined by claims.
Unless otherwise defined, all technology and scientific terminology used by this specification all have this area skill The implication that art personnel's routine understands.In case of conflict, it is as the criterion with the definition of this specification.
In the context of the present specification, in addition to the content clearly stated, anything do not mentioned Preferably or item be the most directly suitable for known in the art those and without carrying out any change.And, herein Any embodiment described all can with one or more other embodiments described herein freely In conjunction with, the technical scheme being consequently formed or technological thought are accordingly to be regarded as the original disclosure of the present invention or original description A part, and be not considered as the new content the most not disclosing or expecting, unless this area Technical staff thinks that this combination is the most unreasonable.
All features disclosed in this invention can in any combination, and these combinations should be understood the present invention Disclosure of that, unless those skilled in the art think that this combination is the most unreasonable.This specification institute Disclosed numerical point, not only includes specifically disclosed numerical point, also includes the end points of each numerical range, The scope of these numerical point institute combination in any is regarded as the published scope of the present invention, no matter herein In whether separately disclose these numerical value pair.
(1) microalgae biomass and the integrated processes of industrial waste gas denitration are produced
1. produce microalgae biomass and an integrated processes for industrial waste gas denitration, comprise the following steps:
(1) step of cultivating microalgae;In this step, at the end of relying on microalgae metabolism to make this step Algae solution is in alkalescence (preferable ph > 8, more preferably pH value is 9~11);
(2) from the algae solution that step (1) is gathered in the crops, microalgae is isolated to obtain microalgae and alkaline residue Step;
(3) from the microalgae that step (2) obtains, fluid composition, protein, carbon hydrate are extracted The step of one of thing, nucleic acid, pigment, vitamin, somatomedin or its combination in any (preferably carries Take the step of one of fluid composition, protein, starch, cellulose or its combination in any);
With
(3) combination of one or both of following step (A), step (B);
(A) alkaline residue obtained by step (2) absorbs the NOx in industrial waste gas, with absorbing NOx After the cultivating microalgae process that solution is step (1) provide nitrogen source step;
(B) it is nitric acid and/or nitrous acid (preferably nitric acid and optional by the NOx conversion in industrial waste gas Nitrous acid), alkaline residue step (2) obtained and described nitric acid and/or nitrous acid are (preferably Nitric acid and optional nitrous acid) mixing, with the microalga cultivation process that this mixed solution is step (1) The step in nitrogen source is provided.
According to the present invention, breeding way can be that auto-trophy is (under light illumination, merely with inorganic carbon source Such as CO2Growth), Heterotrophic culture (Heterotrophic culture refer to merely with organic carbon source grow) or luminous energy Hold concurrently support (luminous energy hold concurrently support refer to, utilize inorganic carbon source such as CO the most simultaneously2Raw with organic carbon source Long).
Micro algae growth needs necessary condition, the most suitable temperature, sufficient illumination (auto-trophy Or luminous energy holds concurrently and supports), enough water, CO2And the nutrient substance such as nitrogenous fertilizer, phosphate fertilizer, in regulation and control algae solution Dissolved oxygen, pH value are in the range of suitably etc..Although for different microalgae, these conditions phase not to the utmost With, but these are all known in the art.
It is said that in general, cultivation temperature is 15~40 DEG C, preferably temperature is 25~35 DEG C;Algae solution pH Value is 6~11, and preferably algae solution pH value is 7~9.Auto-trophy or luminous energy are held concurrently when supporting, and light intensity is 1000~200000 luxs, preferably light intensity are 5000~150000 luxs.
The kind of microalgae is not limited by the present invention.According to the invention it is preferred to cultivate those to be suitable to oil-producing Microalgae, the most both can obtain bioenergy, again can be with exhaust gas emission reduction pollutant.
Support can increase part aquaculture cost because using organic carbon source although Heterotrophic culture or luminous energy are held concurrently, but Its cultivation efficiency also greatly improves, and makes following process process be simplified, therefore if able to avoid nothing Bacterium cultivates, it becomes possible to avoid consuming a large amount of steam and system is carried out stringent sterilization process, thus significantly drop Low aquaculture cost.According to the present invention, particularly preferably those can Heterotrophic culture or luminous energy be held concurrently foster microalgae, Such as chlorella, scenedesmus, spirulina or single needle algae.It is surprising that with Heterotrophic culture or luminous energy When the mode of supporting of holding concurrently cultivates these microalgae, as long as adding a number of EM bacterium, even if not carrying out disinfection Sterilizing, cultivation also can be smoothed out, and the growth rate of microalgae greatly speeds up, even if water source contains in a large number Noxious bacteria and/or unlimited cultivation, result is also such;And when being added without EM bacterium, Heterotrophic culture or Double the supporting of luminous energy would generally be failed.
Hold concurrently according to the present invention, described Heterotrophic culture or luminous energy in supporting, do not carry out disinfecting action (no Carry out steam sterilization and be added without antibacterial), but add EM bacterium.
According to the present invention, carry out Heterotrophic culture or luminous energy and hold concurrently when supporting, available organic carbon source include but not It is limited at least in sugar, organic acid, acylate, alcohol, cellulose hydrolysate and glucidtemns Kind;Such as it is selected from glucose, fructose, acetic acid, sodium acetate, lactic acid, ethanol, methanol, fiber At least one in element hydrolysate and cellulose hydrolysate, preferably selecting is glucose.
Growth pattern according to micro algae biomass and the Expenditure Levels of culture fluid Middle nutrition material, need Supplement not enough nutrient substance in time.According to the present invention, any mode adding nutrient substance is all can , such as segmentation is added or is added continuously, as long as can control the amount of nutrient substance at suitable model In enclosing.
According to the present invention, carry out Heterotrophic culture or luminous energy is held concurrently when supporting, typically by the concentration control of organic carbon source System, in 0.1g/L algae solution~30g/L algae solution, is preferably controlled in 1g/L algae solution~30g/L algae solution, more It is preferably controlled in 2g/L algae solution~10g/L algae solution.Organic carbon source can disposably add, it is also possible to point Repeatedly add.
Described EM bacterium (Effective Microorganisms) belongs to prior art, and it is main By belonging to photosynthetic bacteria group, lactobacillus, yeast flora, Gram positive actinomycetes group, system of fermenting Tens kinds of microorganism compositions of thread flora, are a kind of commercially available active bacteria formulations.Described EM bacterium was both Can prepare voluntarily according to existing knowledge, it is also possible to by commercially available, need before using according to existing knowledge Or the explanation of commercial preparations ferments.
In accordance with the present invention, it was found that EM bacterium has two kinds of functions, one is the growth that can promote microalgae;Two It it is the bacterial reproduction that can suppress microalgae is harmful to.It should be appreciated that it is an object of the invention to obtain microalgae Biomass, therefore the consumption of EM bacterium should meet the needs accelerating micro algae growth, can not be because of consumption mistake Inoperative less, too much nutrient substance can not be consumed because consumption is excessive with microalgae competition again.Appoint The feed postition (such as disposable addition or addition several times) of what EM bacterium and any EM bacterium consumption It is all available, as long as the needs accelerating micro algae growth can be met.
According to the present invention, the addition of EM bacterium is preferably 1 × 106Individual/L algae solution~9 × 108Individual/L Algae solution;More preferably 1 × 107Individual/L algae solution~5 × 108Individual/L algae solution.
In step (2), preferably rely upon microalgae metabolism and make the pH value of algae solution at the end of cultivation 8, more excellent Selecting the pH value of algae solution at the end of relying on microalgae metabolism to make cultivation is 9~11.
The present inventor is found by lot of experiments, holds concurrently foster breeding way for auto-trophy or luminous energy, When microalgae metabolism alkali nitrates, alkali metal nitrites salts, alkali carbonate, alkali metal carbonic acid When one of hydrogen salt, alkali metal phosphate, alkali metal hydrogen phosphate or its combination in any, if at microalgae Breeding process in algae solution, be not passed through CO2Or it is added without pH adjusting agent, then the pH value of algae solution Can rise, especially when microalgae metabolism alkali nitrates, alkali metal nitrites salts or a combination thereof, algae Liquid pH value presents ascendant trend faster.The pH value of general cultivating microalgae is 6~11, works as culture fluid During containing above-mentioned nutrient substance, the model allowed beyond micro algae growth in order to avoid the pH value of culture fluid Enclosing, the present invention is preferably at least with containing CO2Gas be microalgae breeding process part carbon source is provided, logical Cross control containing CO2The intake of gas, can easily the pH value of algae solution be controlled at suitable model In enclosing.Hold concurrently foster breeding way as described previously for auto-trophy or luminous energy, when the culture fluid of microalgae In containing alkali nitrates, alkali metal nitrites salts, alkali carbonate, alkali metal hydrogencarbonate, When one of alkali metal phosphate, alkali metal hydrogen phosphate or its combination in any, if in the cultivation of microalgae During, do not provide or CO is provided less2(or pH adjusting agent), then the pH value of algae solution presents rising Trend.Utilize this phenomenon, can not provide in the cultivating microalgae later stage or CO is provided less2(or PH adjusting agent), the algae solution at the end of relying on microalgae metabolism to make cultivation is alkalescence, thus can utilize The alkaline residue isolating microalgae absorbs the NOx in waste gas or neutralizes the acid solution after fixing NOx, and Required nitrogen source is provided for cultivating microalgae subsequently with it.
Breeding way for Heterotrophic culture, it would however also be possible to employ used with above-mentioned breeding way later stage Identical means, the algae solution at the end of making cultivation is alkalescence.But it is according to the present invention, micro-in heterotrophism cultivation The algae later stage provides illumination, can accelerate this regulation algae solution process in alkalescence.
According to the present invention, aforesaid various alkali metal nutritive salt are preferably the alkali metal battalion of sodium and/or potassium Support salt.
Inventor finds, utilizes the alkaline residue after isolating microalgae can absorb waste gas expeditiously In NOx or acid solution after neutralizing fixing NOx, obtain containing NO3 -And/or NO2 -Solution, This solution directly can provide nitrogen source for next group both culturing microalgae, after this nitrogen source is by microalgae metabolism, Can again make algae solution is alkalescence, can be in both culturing microalgae culture fluid and industry by such a pattern The circulation closed is realized between absorbing liquid or the neutralizer of exhaust gas denitration process, thus by " microalgae is supported Grow " organically connect with " industrial waste gas denitration ", it is possible not only to utilize microalgae by polluted by nitrogen Thing changes into useful biomass expeditiously, and makes " both culturing microalgae " and " exhaust gas denitration " Become two relatively independent processes, it is to avoid influencing each other of the two.
Alkali absorption method is the exhaust gas denitration technique of a kind of maturation, absorbs about utilizing alkaline aqueous solution The research of waste gas NOx is also a lot, and the present invention can use any one of these existing methods. It is known that in order to make NO absorb completely, oxidizing tower can be set up before alkali liquor absorption tower, utilize waste gas In remaining oxygen or add ozone NO is oxidized to NO2, provide optimum oxidation for alkali absorption method Degree (NO2/ NO mol ratio).The catalyst for catalytic oxidation being suitable to different situations is all known in the art , such as with activated carbon, activated carbon fiber, high silicon Na-ZSM-5 molecular sieve or total silicon beta molecule NO is oxidized to NO for catalyst by sieve at normal temperatures2
According to the present invention, step (A) uses alkali absorption method to absorb fixing NOx, is used for absorbing admittedly The absorbing liquid determining waste gas NOx uses the alkaline residue obtained in microalga cultivation process, and 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, but the solution obtained after NOx being absorbed Directly provide nitrogen source for cultivating microalgae.
According to the present invention, step (B) can use any existing method by the NOx in industrial waste gas It is converted into nitric acid and/or nitrous acid, such as nitric acid absorption process, the emulsion formed with water with organic sulfoxide The method absorbing NOx or the method fixing NOx with nitrifier.
Some microalgae can not metabolism NO2 -, when cultivating these microalgae, need to select suitable fixing The method of NOx, so that NOx is largely or entirely converted into NO3 -.According to the present invention, it is known that suitably Method be all available, such as oxidative absorption method with higher concentration nitric acid as absorbent, with dioxygen Water and oxidative absorption method that nitric acid is absorbent or the method fixing NOx with nitrifier.
Can simultaneously metabolism NO according to the invention it is preferred to cultivate those3 -And NO2 -Microalgae, such as this , the most there is not conversion NO in bright chlorella, single needle algae, scenedesmus or the spirulina filtered out2 -Problem.
According to the invention it is preferred to be resistant to the microalgae of high alkali environment, cultivate these microalgae and can enter one Step improves the pH value of alkaline residue, and then improves and nitric acid and/or nitrite reaction or absorb NOx Efficiency.Inventor, through lot of experiments, filters out the following microalgae being capable of withstanding high alkali environment, such as Chlorella, single needle algae, scenedesmus or spirulina, these microalgae can be in the environment of pH be 9~11 Healthy growth.
According to the invention it is preferred to those be not passed through CO2Can be relied on self time (or pH adjusting agent) Metabolism improves rapidly the microalgae of algae solution pH value, cultivates these microalgae and can improve cultivating microalgae further The efficiency of process.Inventor, through lot of experiments, filters out and following can improve rapidly algae solution pH value Microalgae, such as chlorella, single needle algae, scenedesmus or spirulina, above-mentioned microalgae can be little in 1~24 Time interior the pH value of algae solution is brought up to 9~11, make algae solution meet the most anti-with nitric acid and/or nitrous acid The requirement of fixing NOx or should be absorbed.
In the case of You Xuan, in the solution providing nitrogen source for microalgae described in step (3), with nitrogen Atom meter, the amount of nitrogen-containing compound is 0.1~400mmol/L, preferably 10~300mmol/L, Further it is preferably 20~200mmol/L.
In industrial waste gas in addition to containing NOx, may be possibly together with other pollutant such as SOx, ability Field technique personnel are tested (such as by measuring NOx absorbance or measuring micro algae growth by simple The intensity of variation of speed), it becomes possible to confirm whether waste gas contains or excessively contain the present invention The pollutant that make a significant impact of integrated processes.Inventor finds, when in the flue gas of industrial discharge SOx content higher time, the alkaline residue absorption efficiency to NOx can be reduced.As required, ability SOx in waste gas can also be reduced to not show by conventionally known technological means by field technique personnel Write and affect the level that the integrated processes of the present invention is implemented.The flue gas of general industry discharge, especially fires Containing a large amount of SOx in flue-gas, therefore for these industrial waste gases, the waste gas in the present invention is needed to take off Before nitre, the SOx contained removes.
According to the present invention, described industrial waste gas does not preferably contain SOx or processes through desulfurization (de- SOx in removing exhaust gas) industrial waste gas.
It should be appreciated that " both culturing microalgae " and " industrial waste gas denitration " in the present invention is two Relatively independent process, described containing CO2The major function of gas is to provide carbon source for micro algae growth, its It is substantially free of SOx and NOx, or its SOx and/or NOx contained is not enough to affect the present invention Realization.Described containing CO2Gas can be through purified treatment (removing SOx and NOx in waste gas) Industrial waste gas, or be not contain the industrial waste gas of SOx and NOx.
(2) cultivating microalgae and the system of industrial waste gas denitration
A kind of system producing microalgae biomass and industrial waste gas denitration, this system includes:
(1) hold concurrently support unit, Heterotrophic culture unit for the auto-trophy unit of cultivating microalgae, luminous energy One of or their combination in any;
(2) for the algae solution of results being separated into the separative element of microalgae and alkaline residue;
(3) for from microalgae, extract fluid composition, protein, carbohydrate, nucleic acid, The extraction unit of one of pigment, vitamin, somatomedin or its combination in any (preferably extracts line of oils One of compound, protein, carbohydrate or the extraction unit of its combination in any);
(4) with the denitration unit of the NOx in alkali liquor absorption industrial waste gas, by the NOx in industrial waste gas The combination of one or both of the denitration unit being converted into nitric acid and/or nitrous acid;
(5) one or both of following material transport way (A), material transport way (B) Combination;
(A) for the alkaline residue in (2) is mixed with nitric acid and/or the nitrous acid of acquisition in (4) Merge and be delivered to the material transport way of cultivation unit in (1);
(B) for the alkaline residue in (2) being delivered to the material of alkali liquor denitration unit in (4) Transport way, and it is delivered to (1) for described alkali liquor denitration unit absorbing the solution after NOx The material transport way of middle cultivation unit.
According to the present invention, the number of any one unit in (1) can be one or more;Both may be used To be one of open cultivation, enclosed cultivation, it is also possible to be combination.Described light One of pond, raceway pond, bioreactor or combinations thereof can be selected from, preferably by autotrophy unit For pond or raceway pond.It is anti-that the double foster unit of described luminous energy and Heterotrophic culture unit are both preferably photo bio Answer device.
According to the present invention, one preferred embodiment, an at least auto-trophy in (1) Unit, and also luminous energy is held concurrently the combination of one or both of foster unit, Heterotrophic culture unit.This enforcement Mode carries out industrial waste gas denitration and reduction of discharging CO for simultaneously2
According to the present invention, another preferred embodiment is, in (1) for luminous energy hold concurrently support unit, The combination of one or both of Heterotrophic culture unit.This embodiment is mainly used in carrying out Industry Waste QI prostration Nitre.
According to the present invention, the separative element in (2) can be the most existing for algae solution being separated Become microalgae and the separative element of foster algae residual liquid, such as use flocculation, be centrifuged, filter, the mode such as sedimentation One of or combinations thereof separate the unit of algae solution;Preferably employ subsidence style to separate the list of algae solution Unit.
According to the present invention, the extraction unit of (3) can use existing known those.
According to the denitration unit of the NOx used in the present invention, (4) in alkali liquor absorption industrial waste gas, both Can be the denitration unit only with alkali liquor as absorbent, it is also possible to be to be partially absorb agent de-with alkali liquor Nitre unit, such as with alkali liquor/organic sulfoxide emulsion denitration unit as absorbent.
According to the present invention, the NOx conversion in industrial waste gas is nitric acid and/or nitrous acid by (4) Denitration unit, both can be chemistry denitration unit, such as denitration unit with nitric acid as absorbent, with Water/organic sulfoxide emulsion is the denitration unit of absorbent, the denitration as absorbent with hydrogen peroxide and nitric acid Unit;Can also be biological denitrification unit, such as utilize nitrifier to convert the denitration unit of fixing NOx.
According to the present invention, the denitration unit in (4) is preferably and any is arranged at chemical plant installations, especially It it is the denitration unit of oil refining apparatus, petrochemical plant, coal chemical engineering equipment, biochemical industry device.
According to the present invention, the preferred geographical position of whole unit in (1), (2), (3) is close, Such as within the scope of radius 100 kilometers, 50 kilometers, 10 kilometers or 5 kilometers.
According to the present invention, the material transport way described in (4) can be pipeline, vehicle such as vapour Car or train, preferred pipeline carries.
(3) method producing bio-fuel
A kind of method producing bio-fuel, the raw material sources of the method are the oil of step (3) in 1 Compositions.
According to the method for aforementioned production bio-fuel, by selected from distilling, extract, be hydrogenated with, cracking, Isomerization, the group technology of overlapping, be processed into Fuel Petroleum, diesel fuel and jet by fluid composition One or more in fuel.
Described fluid composition is mainly made up of hydrocarbon and/or oils and fats (fatty glyceride), and it is permissible By microalgae simultaneously or successively carries out breaking cellular wall, extracting obtains.Described breaking cellular wall can use existing Technological means completes, and such as utilizes one of heat, mechanical force, alkali, acid, enzyme or combinations thereof to enter Row breaking cellular wall.Described extracting can use organic solvent such as hexane to be stripped, or uses CO2Enter Row supercritical extraction.
When described fluid composition contains material disadvantageous to certain following process, can use but not It is limited to hydrogenation by these devolatilization, such as hydrogenation deoxidation, hydrodenitrogeneration, HDM etc..
Described cracking can be thermal cracking, catalytic cracking such as fluid catalytic cracking, be hydrocracked, Steam cracking or hydrothermal cracking.
With the mixture of described fluid composition or this fluid composition and petroleum hydrocarbon as raw material, by steaming Vapour cracking can obtain low-carbon alkene or the alpha-olefin of more Long carbon chain.Such as use tube cracking furnace, Pyrolysis furnace outlet temperature is 760~860 DEG C, the mass ratio of dilution steam generation and cracking stock be 0.10~ Under conditions of 0.50, the low-carbon alkene of C2~C4 can be produced;Pyrolysis furnace outlet temperature be 560~ Under conditions of 680 DEG C, the mixing alpha-olefin of C6~C24, particularly C6~C12 of high value can be produced Alpha-olefin.
Utilize catalytic cracking, equally obtain low-carbon alkene, such as propylene.
Transesterification technique (transesterification) is utilized to be changed into by fatty glyceride Fatty acid methyl ester.Generally biodiesel is the fatty acid methyl ester of C14~C18, according to the actual needs, May select and distillation unit is set, to obtain suitable fraction as biodiesel.According to actual needs, The optional means such as hydrogenation or blending that use, the stability of raising biodiesel.This biodiesel both may be used To be used alone, it is also possible to be used in mixed way with common diesel.
Can also obtain by described fluid composition being carried out the combined treatment process of deoxidation and hydrogenation Diesel fuel, such as first carries out deoxidation treatment to this fluid composition, then in the presence of high temperature and hydrogen Make double bond saturated by hydrogenation again.
Pass through F-T synthesis, it is possible to obtain the fuel of ultra-low sulfur, such as Fuel Petroleum, diesel oil combustion Material, jet fuel etc..
By the combination of above-mentioned technique, the objectionable impurities in fluid composition can be removed, obtain lighter hydrocarbons, Cracking further to these lighter hydrocarbons, isomerization or overlapping can obtain Fuel Petroleum.
(4) system of bio-fuel is produced
A kind of system producing bio-fuel, including:
(1) selected from distillation unit, extraction unit, hydrogenation unit, Cracking Unit, isomerization unit, The combination of Superposition unit;
System defined in (2) 15;
(3) for the fluid composition obtained in (2) being delivered to the material conveying of unit in (1) Approach.
According to the present invention, the preferred geographical position of whole unit in (1), (2) is close, such as exists Within the scope of radius 100 kilometers, 50 kilometers, 10 kilometers or 5 kilometers.
According to the present invention, the material transport way described in (3) can be pipeline, vehicle such as vapour Car or train, preferred pipeline carries.
The present invention has constructed a kind of circulation warp reducing discharging industrial waste gas pollutant and production microalgae biomass Ji pattern.Utilize the NO in the waste gas of industrial dischargexThe nitrogen source being used as in culture fluid, is reducing discharging dirt While dye thing, it is thus achieved that valuable microalgae biomass.In the pattern of such a recycling economy, The departmental cost administering industrial waste gas is used for cultivating microalgae, and factory decreases waste gas, discharge of wastewater and right The pollution of environment, defines the circulation of closing, outlet only microalgae biomass.
The present invention is described in detail below by embodiment.
Algae solution optical density value (OD680Value) measure: optical density value spectrophotometric determination, with distillation Water compares, and measures algae solution light absorption value at wavelength 680nm, as the index of microalgae concentration.
The mensuration of solution nitrogen content: use ICS3000 type ion chromatograph (Dionex company of the U.S.) Measure the NO in aqueous solution3 -Content or NO2 -Content, instrument be furnished with EG40 leacheate automatic generator, Electric conductivity detector and chameleon chromatographic work station;IonPac AS11-HC type detached dowel (250mm × 4mm i.d.);IonPac AG11 type guard column (50mm × 4mm i.d.);ASRS-ULTRA anion Self suppressor.Leacheate: KOH solution;Flow velocity is 1mL/min;Eluent concentration: 30mmol/L; Sample size is 60 μ L;Column temperature is 30 DEG C;Suppression electric current 100mA;External standard method peak area quantification.
Count of bacteria: carry out count of bacteria according to the following steps
1. sample washing: draw 1ml sample, washs 2-3 time with 1 × PBS;2. initial gross separation: According to algae and the difference of antibacterial centrifugal force, first it is centrifuged 2min, initial gross separation algae with 1000rpm (, in supernatant, algae is in precipitation for antibacterial);If algae content is higher, again repeat;3. Collecting supernatant, now the amount of algae in supernatant is negligible, and 8000rpm is centrifuged 5min, abandons Clearly;4. by the 500ul antibacterial resuspended precipitation of rupture of membranes agent, room temperature reaction 15min;5.8000rpm it is centrifugal 5min, washs 2 bacterium solution with 1 × PBS;6. add the resuspended thalline of 100ul 1 × PBS, add 5ul PI dye liquor mother solution, room temperature reaction 30min;7. fluorescence microscopy Microscopic observation antibacterial counting, 4 In individual block plaid, bacterial number is up to 1000, during more than 1000, dilutes bacterium solution certain multiple Again count;8. computing formula:
Bacterial density=count results/4 × extension rate × 4 × 10 in surveyed solution4Individual/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 cultivates level, aseptic) Sharp that health Cat No.REK3013
Cell climbing sheet NEST
Key instrument:
Instrument Manufacturer
Counting chamber Shanghai precision instrument
Fluorescence microscope Olympus BX-51
The culture medium of microalgae: medium component is shown in Table 1~table 4.
Table 1 culture medium BG11
Component Composition, mg/L
K2HPO4·3H2O 40
NaNO3 1500
Na2CO3 20
MgSO4·7H2O 75
CaCl2·2H2O 36
Citric acid 6
Ferric ammonium citrate 6
EDETATE SODIUM 1
Trace element A5 1
Table 2 trace element A5
Component Composition, mg/L
H3BO3 2860
MnCl2·4H2O 1810
ZnSO4·7H2O 222
CuSO4·5H2O 79
NaMoO4·5H2O 390
Co(NO3)2·6H2O 50
Table 3 Heterotrophic culture base
Table 4 trace element
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: probiotic bacteria used in embodiment be Kang Yuan oasis bio tech ltd produce as Gold probiotic bacteria, carries out activation process, PH < 4 by its explanation before using.
Embodiment 1
The present embodiment is used for " adding the impact photoautotrophic on microalgae of EM bacterium " is described.
Use BG11 culture medium (adding nutritional labeling by table 1, culture fluid does not carry out sterilization treatment) Cultivate chlorella (from Sinopec microalgae algae kind storehouse, numbering Chlorella sp.RIPP-1), control Temperature processed is between 20~30 DEG C, is passed through compressed air and CO2Cultivate, when algae solution PH > 10 time be passed through CO2, when algae solution PH < stops when 7.5 being passed through CO2.Incubation use natural daylight cultivate, daytime Intensity of illumination reaches as high as 60000 luxs, detects the OD of algae solution every day680Value, cultivates 14 continuously Gather in the crops after it, cultivate and terminate within first 1 day, to stop being passed through containing CO2Gaseous mixture, terminate cultivation after, pass through It is centrifugally separating to obtain algae mud and foster algae residual liquid.The growth curve of microalgae is shown in Fig. 1, two examinations in Fig. 1 That tests differs only in: one of them test is without EM bacterium, and another test is by 3.6 × 106Individual The addition of/L algae solution adds EM bacterium.For adding the test of EM bacterium, breeding process is monitored algae solution Count of bacteria < 6.7 × 106Individual/mL algae solution, at the end of recording cultivation, algae solution pH is increased to 9.8 naturally. It can be seen from figure 1 that under the conditions of auto-trophy, add EM bacterium and promote the growth of microalgae.
Embodiment 2~5 is used for " luminous energy is held concurrently in supporting, the impact on microdisk electrode of the EM bacterium addition " is described.
Embodiment 2
Use BG11 culture medium (adding nutritional labeling by table 1, culture fluid does not carry out sterilization treatment) Cultivate chlorella (from Sinopec microalgae algae kind storehouse, numbering Chlorella sp.RIPP-1), Incubation adds the glucose of 2g/L, and controlling temperature is between 20~30 DEG C, is passed through compressed air With CO2Cultivate, when algae solution PH > 10 time be passed through CO2, when algae solution PH < stops when 7.5 being passed through CO2。 Using natural daylight to cultivate in incubation, daylight intensity reaches as high as 60000 luxs, Detect the OD of algae solution every day680Value, the growth curve of microalgae is shown in Fig. 2.Wherein EM addition is 3.6×106Individual/L algae solution, monitors the count of bacteria < 8 × 10 of algae solution in breeding process6Individual/mL algae solution, Gather in the crops after cultivating 14 days continuously, cultivate and terminate within first 1 day, to stop being passed through CO2Flue gas, and make algae solution pH Naturally it is increased to 9.4, then terminates cultivation, be centrifugally separating to obtain algae mud and foster algae residual liquid.
Embodiment 3
The present embodiment differs only in embodiment 2: EM addition is 1.8 × 107Individual/L algae solution. Breeding process is monitored the count of bacteria < 1 × 10 of algae solution7Individual/mL algae solution, records algae at the end of cultivation The pH of liquid is increased to 9.3 naturally.The growth curve of microalgae is shown in Fig. 2.
Embodiment 4
The present embodiment differs only in embodiment 2: EM addition is 3.6 × 107Individual/L algae solution. Breeding process is monitored the count of bacteria < 2 × 10 of algae solution7Individual/mL algae solution, records algae at the end of cultivation The pH of liquid is increased to 8.9 naturally.The growth curve of microalgae is shown in Fig. 2.
Embodiment 5
The present embodiment differs only in embodiment 2: EM addition is 7.2 × 107Individual/L algae solution. Breeding process is monitored the count of bacteria < 5.8 × 10 of algae solution7Individual/mL algae solution, at the end of recording cultivation The pH of algae solution is increased to 8.7 naturally.The growth curve of microalgae is shown in Fig. 2.
Comparative example 1
This comparative example differs only in embodiment 2: without EM bacterium.Breeding process is monitored The count of bacteria of algae solution has been up to 1.2 × 108Individual/mL algae solution, records algae solution at the end of cultivation PH is increased to 7.9 naturally.The growth curve of microalgae is shown in Fig. 2.
It can be seen in fig. 2 that under the conditions of luminous energy is held concurrently and supported, add EM bacterium and promote the growth of microalgae.
Embodiment 6~8 is used for " microalgae metabolism to NO3-N and NO2-N " is described.
Embodiment 6
Use BG11 culture medium (adding nutritional labeling by table 1, culture fluid does not carry out sterilization treatment) Cultivate chlorella (from Sinopec microalgae algae kind storehouse, numbering Chlorella sp.RIPP-1), Controlling temperature is between 20~30 DEG C, is passed through compressed air and CO2Cultivate, when algae solution PH > 10 time logical Enter CO2, when algae solution PH < stops when 7.5 being passed through CO2.Incubation use natural daylight cultivate, Daylight intensity reaches as high as 60000 luxs, detects the OD of algae solution every day680Value, trains continuously Support 14 days.The growth curve of microalgae is shown in Fig. 3.
Embodiment 7
The present embodiment differs only in embodiment 6: the sodium nitrate of 1.5g/L in culture medium replaced Change 1.35g sodium nitrite and 0.15g sodium nitrate into.The growth curve of microalgae is shown in Fig. 3.
Embodiment 8
The present embodiment differs only in embodiment 7: cultivating microalgae is that single needle algae is (from China Petrochemical industry microalgae algae kind storehouse, numbering Monoraphidium dybowskii.RIPP-50).Microalgae Growth curve is shown in Fig. 3.
It can be seen from figure 3 that use the microalgae algae kind of institute's selection-breeding, nitrate and nitrous can be utilized simultaneously Hydrochlorate preferably grows.
Embodiment 9~16 is used for illustrating that " in the case of a large amount of interpolation organic carbon sources, EM bacterium is to micro- The impact that algae metabolism is inorganic nitrogen-sourced ".
Embodiment 9
Initially with BG11 culture medium, (adding nutritional labeling by table 1, culture fluid is not carried out at sterilizing Reason) cultivate chlorella (from Sinopec microalgae algae kind storehouse, numbering Chlorella sp.RIPP-1); Work as OD680When value is 4, add a Heterotrophic culture base nutritional labeling by table 3 ormal weight.Control temperature Degree is between 20~30 DEG C, is passed through compressed air and CO2Cultivate, when algae solution PH > 10 time be passed through CO2, When algae solution PH < stops when 7.5 being passed through CO2.In incubation use natural daylight cultivate, daytime light Reach as high as 60000 luxs according to intensity, add the glucose of 2g/L, and by 2.9 × 107Individual/L The amount of algae solution adds EM bacterium, detects the OD of algae solution every day680Value;10g/L is again added after cultivating 1 day Glucose, and by 3.6 × 107Individual/L algae solution adds EM bacterium;Again add when cultivating to the 5th day Glucose 10g/L, the count of bacteria monitoring algae solution in breeding process is up to 9.7 × 106Individual/mL algae Liquid, gathers in the crops after cultivating 8 days continuously, stops being passed through CO after last addition glucose2, terminate to support When growing, algae solution pH value is 8.6, is centrifugally separating to obtain algae mud and foster algae residual liquid.Analyze and support in algae residual liquid NO3 -With NO2 -Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 4.
Embodiment 10
The present embodiment differs only in embodiment 9: cultivating microalgae is that single needle algae is (from China Petrochemical industry microalgae algae kind storehouse, numbering Monoraphidium dybowskii.RIPP-50).Cultivated The count of bacteria monitoring algae solution in journey has been up to 4.6 × 107Individual/mL algae solution, records cultivation and terminates Time algae solution pH be naturally increased to 8.2, analyze the NO supported in algae residual liquid3 -With NO2 -Total content < 200 μg/g.The growth curve of microalgae is shown in Fig. 4.
Embodiment 11
The present embodiment and embodiment 9 differ only in following aspect: primary EM bacterium addition It is 7.9 × 107Individual/L algae solution, without secondary EM bacterium;And the glucose that second time is added Amount is 30g/L, without third time glucose.The count of bacteria monitoring algae solution in breeding process is the highest It is 2.6 × 107Individual/mL algae solution, at the end of recording cultivation, the pH of algae solution is increased to 8.2 naturally, point The NO in algae residual liquid is supported in analysis3 -With NO2 -Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 4.
Embodiment 12
The present embodiment differs only in embodiment 11: cultivating microalgae is that single needle algae is (from China Petrochemical industry microalgae algae kind storehouse, numbering Monoraphidium dybowskii.RIPP-50).Cultivated The count of bacteria monitoring algae solution in journey has been up to 5.2 × 107Individual/mL algae solution, records cultivation and terminates Time algae solution pH be naturally increased to 7.8, analyze the NO supported in algae residual liquid3 -With NO2 -Total content < 200 μg/g.The growth curve of microalgae is shown in Fig. 4.
Comparative example 2
This comparative example differs only in embodiment 9: without EM bacterium.In monitoring incubation Algae solution count of bacteria is up to 13.6 × 108Individual/mL algae solution, records the pH of algae solution at the end of cultivation Naturally 7.2 it are increased to.The growth curve of microalgae is shown in Fig. 4.
As can be seen from Fig. 4, add EM bacterium the growth of microalgae is greatly facilitated and consumes rapidly inorganic Nitrogen source.
Embodiment 13
Initially with BG11 culture medium, (adding nutritional labeling by table 1, culture fluid is not carried out at sterilizing Reason) cultivate chlorella;Work as OD680When value is 4, add a Heterotrophic culture base by table 3 ormal weight Nutritional labeling.Controlling temperature is between 20~30 DEG C, is passed through compressed air and CO2Cultivate, work as algae solution It is passed through CO during PH > 102, when algae solution PH < stops when 7.5 being passed through CO2.Incubation uses nature Daylight is cultivated, and daylight intensity reaches as high as 60000 luxs, first existing after chlorella inoculation Cultivate 2 days under illumination autotrophic condition, then add the glucose of 2g/L, and by 1.8 × 108Individual/L The amount of algae solution adds EM bacterium, detects the OD of algae solution every day680Value;10g/L is again added after cultivating 3 days Glucose, and by 1.8 × 108Individual/L algae solution adds EM bacterium;Fructus Vitis viniferae is again added after cultivating 2 days Sugar 10g/L, the count of bacteria monitoring algae solution in breeding process is up to 2.9 × 107Individual/mL algae solution, Gather in the crops after cultivating 14 days continuously, stop being passed through CO after last addition glucose2, terminate cultivation Time algae solution pH value be 9.2, be centrifugally separating to obtain algae mud and foster algae residual liquid.Analyze and support in algae residual liquid NO3 -With NO2 -Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 5.
Embodiment 14
The present embodiment differs only in following aspect with embodiment 13: without secondary EM Bacterium;And the glucose amount that second time is added is 30g/L, without third time glucose.Cultivated The count of bacteria monitoring algae solution in journey is up to 2.9 × 107Individual/mL algae solution, records algae at the end of cultivation The pH of liquid is increased to 9.3 naturally, analyzes the NO supported in algae residual liquid3 -With NO2 -Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 5.
Embodiment 15
The present embodiment differs only in embodiment 13: NaNO in BG11 culture medium3Replace with KNO3, And KNO3Addition is 0.5g/L.The count of bacteria monitoring algae solution in breeding process is up to 1.3×107Individual/mL algae solution, recording the pH value of algae solution when terminating cultivation is 9.4, analyzes and supports algae residual liquid In NO3 -With NO2 -Total content < 10 μ g/g.The growth curve of microalgae is shown in Fig. 5.
Embodiment 16
The present embodiment differs only in embodiment 14: the NaNO in BG11 culture medium3Replace with KNO3, and KNO3Addition is 0.5g/L.The count of bacteria monitoring algae solution in breeding process is up to 1.7×107Individual/mL algae solution, recording the pH value of algae solution when terminating cultivation is 9.3, analyzes and supports algae residual liquid In NO3 -With NO2 -Total 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, add EM bacterium and all promote micro- The growth of algae.
Embodiment 17~18 is used for illustrating " to utilize the alkaline residue supporting algae acquisition to absorb NOx and with inhaling Receive the solution after NOx and continue the situation of cultivating microalgae ".
Embodiment 17
Use O3Auxiliary law absorbs NOx.
Use NO2Simulating actual flue gas with the gaseous mixture of NO, with compressed air as carrier gas, NOx flow is 0.3L/min, containing O3The XM-Y type that produces from Qingdao Xin Mei cleaning equipment company limited of gas move Dynamic ozonator, flow is 1L/min, makes total flow reach 150L/h, measure entrance after mixing air With the NOx concentration of exit gas, it is calculated as follows NOx absorbance;
NOx absorbance=(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 600 mg/m3, NO2Content is about 20mg/m3)
Flow chart is shown in Fig. 6, wherein absorption tower diameter 100mm, and high 700mm, tower bottom is equipped with sieve-mesh Gas distributor, wherein holds the foster algae residual liquid that 3L embodiment 16 produces.During operation, NOx is mixed Gas is passed directly into absorption tower, absorbs 22h and stops operation, taken out by the foster algae residual liquid in washing tower (for removing CO2), surveys Fixed NO therein3 -With NO2 -Total content be 5900 μ g/g.
Utilize NOx absorbing liquid cultivating microalgae.
Using above-mentioned NOx absorbing liquid as micro algae culturing liquid, denitrogenate other nutrient substance outside source by BG11 Culture medium provides, and cultivates chlorella, and the remainder of cultural method is with embodiment 16, in breeding process The count of bacteria of monitoring algae solution is up to 1.8 × 107Individual/mL algae solution, gathers in the crops after cultivating 14 days continuously, Stop being passed through CO after last addition glucose2, terminating algae solution pH value during cultivation is 9.1, centrifugal Isolated algae mud and foster algae residual liquid.Analyze the NO supported in algae residual liquid3 -With NO2 -Total content < 10 μ G/g, from figure 7, it is seen that use NOx absorbing liquid for cultivation nutritional solution, can promote after adding EM bacterium The growth of microalgae, again by the NO in algae solution3 -And NO2 -Sponge, and return to alkalescence, from And the alkaline absorption solution of exhaust gas denitration can be further used as.
Embodiment 18
Absorb NOx as described in Example 17, the difference is that only: absorption tower holds embodiment 10 3L obtained support algae residual liquid.After absorbing 22h, the foster algae residual liquid in washing tower (for removing CO2) is taken out, measures it In NO3 -With NO2 -Total content be 5800 μ g/g.
Utilize NOx absorbing liquid cultivating microalgae.
Using above-mentioned NOx absorbing liquid as micro algae culturing liquid, denitrogenate other nutrient substance outside source by BG11 Culture medium provides, and cultivates single needle algae, and the remainder of cultural method is with embodiment 10, in breeding process The count of bacteria of monitoring algae solution is up to 9.2 × 106Individual/mL algae solution, gathers in the crops after cultivating 8 days continuously, Stop being passed through CO after last addition glucose2Flue gas, terminating algae solution pH value during cultivation is 8.7, It is centrifugally separating to obtain algae mud and foster algae residual liquid.Analyze the NO supported in algae residual liquid3 -With NO2 -Total content < 200 μ g/g, as can be seen from Fig. 8, using NOx absorbing liquid is cultivation nutritional solution, after adding EM bacterium The growth of microalgae can be promoted, again by the NO in algae solution3 -And NO2 -Sponge, and return to alkali Property, such that it is able to be further used as the alkaline absorption solution of denitration.
Embodiment 19 is used for illustrating " EM bacterium on microalgae without photoheterotrophic impact ".
Embodiment 19
The present embodiment differs only in embodiment 9: cultivate under no light condition.Record end to support When growing, the pH value of algae solution is 7.7.The growth curve of microalgae is shown in Fig. 9.
Comparative example 3
This comparative example is used for " the EM bacterium absorption and assimilation situation to NOx " is described.
This comparative example and the following aspect that differs only in of embodiment 9: simple cultivation EM bacterium;Cultivate Before culture fluid is carried out sterilization treatment;Culture medium still uses BG11 (table 1), but NO3 -Initial concentration For 6900ug/g;Cultivate 14 days.Analyze the NO at the end of cultivating3 -And NO2 -Total content is 5600ug/g. Visible, EM bacterium is far below microalgae to inorganic nitrogen-sourced wear rate in growth course.
Embodiment 20
The present embodiment is used for illustrating that supporting algae residual liquid by alkalescence absorbs NOx.
The alkalescence of Example 14 supports algae residual liquid 3L;Analyze this alkalescence support the potassium in algae residual liquid, sodium from Sub-concentration, preparation has the aqueous solution 3L of identical potassium concentration and Na ion concentration, pairing the moon with it Ion is HCO3 -And CO3 2-, the pH value of water solution prepared is 9.27, supports with the alkalescence of embodiment 14 The pH value of algae residual liquid is essentially identical.The aqueous solution of algae residual liquid and preparation is supported for inhaling respectively with above-mentioned alkalescence Receive liquid, use the method for embodiment 17 to absorb NOx, the absorption efficiency curve of NOx is shown in Figure 10.
As seen from Figure 10, the algae residual liquid absorbance to NOx is supported apparently higher than the alkali liquor prepared.

Claims (20)

1. produce microalgae biomass and an integrated processes for industrial waste gas denitration, comprise the following steps:
(1) step of cultivating microalgae;In this step, at the end of relying on microalgae metabolism to make this step Algae solution is alkalescence;
(2) from the algae solution that step (1) is gathered in the crops, microalgae is isolated to obtain microalgae and alkaline residue Step;
(3) from the microalgae that step (2) obtains, fluid composition, protein, carbon hydrate are extracted One of thing, nucleic acid, pigment, vitamin, somatomedin or the step of its combination in any;
With
(4) combination of one or both of following step (A), step (B);
(A) alkaline residue obtained by step (2) absorbs the NOx in industrial waste gas, with absorbing NOx After the cultivating microalgae process that solution is step (1) provide nitrogen source step;
(B) it is nitric acid and/or nitrous acid by the NOx conversion in industrial waste gas, by step (2) The alkaline residue arrived mixes with described nitric acid and/or nitrous acid, is step (1) with this mixed solution Microalga cultivation process provides the step in nitrogen source.
Method the most according to claim 1, the breeding way in (1) be Heterotrophic culture and/or Luminous energy is held concurrently and is supported.
Method the most according to claim 2, it is characterised in that the organic carbon source used is selected from Sugar, organic acid, acylate, alcohol, cellulose hydrolysate and with at least one in glucidtemns.
The most according to the method in claim 2 or 3, it is characterised in that by organic carbon source used Concentration control in 0.1g/L algae solution~30g/L algae solution.
Method the most according to claim 1, it is characterised in that breeding way be auto-trophy or Luminous energy is held concurrently when supporting, and light intensity is 1000~200000 luxs.
Method the most according to claim 1, it is characterised in that breeding way be auto-trophy or Luminous energy is held concurrently when supporting, with containing CO2Gas as inorganic carbon source.
Method the most according to claim 6, it is characterised in that described containing CO2Gas be warp Cross the industrial waste gas of purified treatment, or be the industrial waste gas not containing SOx and NOx.
8. according to the arbitrary described method of claim 1~7, it is characterised in that in step (3), In the described solution that nitrogen source is provided for microalgae, in terms of nitrogen-atoms, the amount of nitrogen-containing compound be 0.1~ 400mmol/L。
Method the most according to claim 1, it is characterised in that described industrial waste gas is not for containing The industrial waste gas having SOx or the industrial waste gas processed through desulfurization.
Method the most according to claim 1, it is characterised in that in the cultivating microalgae later stage, no There is provided or CO is provided less2Or pH adjusting agent, at the end of relying on microalgae metabolism alkali metal nutritive salt to make cultivation Algae solution be alkalescence;Described alkali metal nutritive salt be alkali nitrates, alkali metal nitrites salts, One of alkali carbonate, alkali metal hydrogencarbonate, alkali metal phosphate, alkali metal hydrogen phosphate or Combinations thereof.
11. methods according to claim 1, it is characterised in that the breeding process of step (1) In, in algae solution, add EM bacterium.
12. methods according to claim 11, it is characterised in that the addition of EM bacterium is 1 ×106Individual/L algae solution~9 × 108Individual/L algae solution, preferably 1 × 107Individual/L algae solution~5 × 108Individual/L Algae solution.
13. methods according to claim 1, it is characterised in that described microalgae be chlorella or Cyanophyceae.
14. methods according to claim 1, it is characterised in that cultivation temperature is 15~40 DEG C, Algae solution pH value is 6~11.
15. 1 kinds of systems producing microalgae biomass and industrial waste gas denitration, this system includes:
(1) hold concurrently support unit, Heterotrophic culture unit for the auto-trophy unit of cultivating microalgae, luminous energy One of or their combination in any;
(2) for the algae solution of results being separated into the separative element of microalgae and alkaline residue;
(3) for from microalgae, extract fluid composition, protein, carbohydrate, nucleic acid, One of pigment, vitamin, somatomedin or the extraction unit of its combination in any;
(4) use (2) neutral and alkali residual liquid absorbs the denitration unit of the NOx in industrial waste gas, by industry NOx conversion in waste gas is the combination of one or both of the denitration unit of nitric acid and/or nitrous acid;
(5) one or both of following material transport way (A), material transport way (B) Combination;
(A) for the alkaline residue in (2) is mixed with nitric acid and/or the nitrous acid of acquisition in (4) Merge and be delivered to the material transport way of cultivation unit in (1);
(B) for the alkaline residue in (2) being delivered to the material of alkali liquor denitration unit in (4) Transport way, and it is delivered to (1) for described alkali liquor denitration unit absorbing the solution after NOx The material transport way of middle cultivation unit.
16. 1 kinds of methods utilizing Ethanol Production by Biomass Fermentation, it is characterised in that raw material is by right The method requiring 1 prepares.
17. 1 kinds of methods producing protein fibre, it is characterised in that raw material is claim 1 The protein that method prepares.
18. 1 kinds of methods producing bio-fuel, it is characterised in that raw material is the side of claim 1 The fluid composition that method prepares.
19. methods according to claim 18, it is characterised in that by selected from distilling, taking out Carry, be hydrogenated with, cracking, isomerization, the group technology of overlapping, fluid composition is processed into Fuel Petroleum, One or more in diesel fuel and jet fuel.
20. 1 kinds of systems producing bio-fuel, including:
(1) selected from distillation unit, extraction unit, hydrogenation unit, Cracking Unit, isomerization unit, The combination of Superposition unit;
(2) system defined in claim 15;
(3) for the fluid composition obtained in (2) being delivered to the material conveying of unit in (1) Approach.
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