CN103013833B - Novel high pH induction and carbon dioxide emission reduction coupling microalgae harvesting method - Google Patents
Novel high pH induction and carbon dioxide emission reduction coupling microalgae harvesting method Download PDFInfo
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Abstract
The invention discloses a novel high pH induction and carbon dioxide emission reduction coupling microalgae harvesting method. Microalgae cells are self-settled and efficiently concentrated by using high pH induction so that high-efficiency and low-cost harvesting is realized. A CO2 emission reduction carbon replenishing technology is coupled, acidic gas CO2 is efficiently absorbed by using harvested high-alkali supernate to ensure that the pH of the high-alkali supernate is reduced to be a level (pH>=8.2) suitable for microalgae growth, high-efficiency carbon replenishing of a culture medium is realized, the supernate after havesting can be recycled, and the harvesting cost and fertilizer cost during large-scale cultivation of the microalgae are greatly lowered.
Description
Technical field:
The present invention relates to a kind of collecting method of micro-algae culture, the micro-algae that is specifically related to a kind of high pH induction, the coupling carbon dioxide discharge-reduction novel method of gathering.
Background technology:
Micro-algae is nutritious, and the materials such as rich in proteins, VITAMIN and polyunsaturated fatty acid have fabulous application prospect at industrial circles such as protective foods, biological feed, medicine and biofuels.But the key issue that hinders at present micro-algae industry development is that cultivation production cost is too high, and the cost of gathering is one of principal element limiting micro-algae cultivation cost.In micro-algae is cultivated, by chemical flocculation, in culture, add macromole or the micromolecular compound that can make on a small quantity cell flocculation, concentrating cells, and then centrifugal or filter and realize cell harvesting to concentrating cells, is the most frequently used collecting method at present.Although the method has higher thickening efficiency to microalgae cell, offset the cost that flocculation concentration cell reduces but chemical floc or flocculation agent cost taken by themselves are too high, human body or animal are had toxic byproduct and hinder the later use exploitation of micro-algal biomass resource, microalgae cell growth is had and poisoned or the substratum (supernatant liquor) of restraining effect after making to gather is difficult to be cycled to used in both culturing microalgae, caused the waste of substratum.And in micro-algae large scale culturing, owing to adding chemical floc, and all flocculation agents at least all can suppress to cultivate the growth of micro-algae, thereby substratum after gathering certainly will be discharged on a large scale, will cause serious environmental problem, the eutrophication problem that the environmental security bringing comprising flocculation agent and medium nutrient content bring.Therefore, in sum, very big must restriction received in further popularization and the amplification of chemical flocculation on micro-algae harvesting technique.And micro-algae harvesting technique of setting up by physical methods such as electricity, magnetic, ultrasonic wave not only exists the problems such as efficiency is on the low side, power consumption is higher, not yet set up proven technique.Micro-algae of therefore, developing a kind of green high-efficient gather pretreatment process be micro-algae industrialization further develop the problem that must solve.
In recent years, have and report and can supplement alkali lye and improve fast the pH of culture by a large amount of, effectively the flocculation concentration of frustule in inducing culture thing, realize less energy-consumption and gather, the high pH substratum (supernatant liquor) after gathering can make the substratum can recycle by acid neutralization substratum.The method still there is higher cost problem, but because the pH scope of the optimum growh of the unicellular micro-algae of majority of cultivating at present approaches neutral (6.5-7.5), therefore, the cost that adds alkali induction is higher, and after gathering in and the acid that adds in a large number of pH comprise hydrochloric acid, sulfuric acid or carbonic acid gas, can increase again new cost.Meanwhile, if the method is used in hydrochloric acid and sulfuric acid and high pH gathers supernatant liquor, although can reduce to a certain extent the discharge of substratum, recycle substratum, along with extend cycling time, can increase substantially the salinity in culture, suppresses the growth of cell.Add carbonic acid gas seemingly wherein comparatively reasonably to select, supplementary carbon source in poikilohaline situation can not changed, but the cost that adds alkali lye is still higher, and carbonic acid gas is weak acid after dissolving in water, addition is large, and the acidifying terminal pH(6.5-7.5 that is suitable micro algae growth), within the scope of this, dissolve in the CO of substratum
2can overflow in a large number, cause carbon source waste.
Summary of the invention:
The object of this invention is to provide one and can make micro-algae automatic sedimentation, micro-algae of low cost, the high pH induction of efficiently mending carbon, environmental protection and the growth of favourable frustule long-term cultivation, coupling carbon dioxide discharge-reduction novel method of gathering.
Novel method that high pH of the present invention induces, micro-algae of coupling carbon dioxide discharge-reduction is gathered has adopted the lower frond automatic sedimentation of high pH induction, for frond centrifugation subsequently provides the algae liquid of high density, not only effectively reduce the highly energy-consuming problem in recovery process in the past, nor can impact downstream processing technique.In the high-alkali supernatant liquor obtaining in separation, adopt coupling CO simultaneously
2reduce discharging and mend carbon technique, not only make high-alkali supernatant liquor capable of circulation for micro-algae cultivation, and improved CO
2mend mass-transfer efficiency (the acid CO of carbon
2gas mass-transfer efficiency in basic solution is high), greatly reduce micro-algae industrial production cost and fertilizer cost, thereby realized object of the present invention.
Micro-algae of high pH induction of the present invention, coupling carbon dioxide discharge-reduction novel method of gathering, is characterized in that, selects optimum growh pH value in 8.2≤pH≤12.3 scope, adaptation high alkalinity, with HCO
3 -for micro-algae of main carbon source the good pH drift characteristic of tool is as algae kind, it is carried out to cellar culture with the substratum of micro-algae, the inorganic carbon source in described substratum is with HCO
3 -be main, CO is used in initial pH>=8.2 of substratum in culturing process
2the pH value of controlling culture system is between 8.2 ~ 9.5, gathers after concentration when microalgae density reaches suitable, stops supplementing CO
2no longer control the pH value of culture system, under the driving of microalgae cell photosynthetic carbon fixation effect or not only under the driving of microalgae cell photosynthetic carbon fixation effect but also add alkali lye the pH value of culture is risen between pH10 ~ 12.3, induction microalgae cell is from sedimentation, microalgae cell precipitation concentrates in bottom of culture vessel, upper strata nutrient solution is progressively clarified, lower floor's microalgae cell precipitation is separated with the high-alkali supernatant liquor in upper strata, the microalgae cell being precipitated thus and high-alkali supernatant liquor, then fill into CO in high-alkali supernatant liquor
2its pH value is reduced to the pH value level of suitable micro algae growth, supplements because microalgae cell is grown other nutritive substances of consuming and carries out recycle as new substratum and cultivate micro-algae simultaneously.
Described selection optimum growh pH value 8.2≤pH≤12.3 scope, adapt to high alkalinity, with HCO
3 -for micro-algae of main carbon source the good pH drift characteristic of tool is as algae kind, its algae kind is preferably basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain, and this basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain is at document: Xiang Wenzhou, Xie Ke, Wu Hualian, He Hui, Xiao Wei, a kind of microscopy of green alga isolate, [J]. Tropical Ocean journal, 2007,26(2), disclosed in 65 ~ 68.This basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain the applicant also hold, and ensure provides to the public in 20 years from the applying date.
The substratum of described micro-algae is conventional micro-algae culture medium, and just its inorganic carbon source is with HCO
3 -be main.Can adopt seawater, artificial seawater, fresh water, degree of saltiness water, fresh water, alkali lake water, salt lake saline or Bittern of Salt Pan for basis preparation, the inorganic carbon source of substratum is with HCO
3 -be main, add concentration>=0.1mM; Initial pH>=8.2 of culture, substratum salinity scope is quality volume fraction 0-300 ‰.In substratum inorganic nitrogen-sourced can be in nitric nitrogen, ammonium nitrogen or urea any a kind or 3 between arbitrary combination, interpolation concentration is 0 ~ 200mM.In substratum, adding phosphoric acid and phosphoric acid salt is inorganic phosphorous sources, and adding concentration is 0 ~ 2000 μ M.In substratum, ferro element is divalence or trivalent inorganic molysite, and adding concentration is 0 ~ 200 μ M.Then in above-mentioned substratum, add as required necessary organism, mainly include waste water, waste residue that machine acid, carbohydrate, peptide class, amino acid, Nucleotide, alkaloid etc. are rich in the organism of carbon, nitrogen element or are rich in the industries such as the agricultural, cultivation, biological products processing, foodstuffs industry, fermentation industry of the elements such as carbon, nitrogen, phosphorus.Be preferably ZSNT substratum (substratum of the prior art, its formula is shown in to civilian continent, Xie Ke, Wu Hualian, He Hui, Xiao Wei, a kind of microscopy of green alga isolate, [J]. Tropical Ocean journal, 2007,26(2), 65 ~ 68), its NaHCO
3for 5g/L.
Micro-algae culture vessel or facility comprise the bioreactor of any shapes such as raceway pond, circle pond and pillar, tubular type, flat, pot type, pocket type or structure, culture adopts the modes such as turbine stirrer, cantilever type stirrer, bubbling inflation to stir, and cultivation light source is sunlight, LED lamp, incandescent light, light pipe.After micro-algae inoculation, first adopt a step culture method to make culture biomass (dry weight) concentration reach the scope (0.5 ~ 50gL that can gather
-1), then adopt semicontinuous training method constantly synchronously carry out gathering intermittence, intermittently supplement the nutrients thing intermittent cyclic to utilize substratum.Lower floor of the present invention microalgae cell precipitation separates and can adopt decantation or water pump extraction method to proceed in other containers or pond with the high-alkali supernatant liquor in upper strata, concentrated lower floor's microalgae cell precipitation proceeds to by water pump the container of gathering and collects, repetitive operation natural subsidence-supernatant liquor shifts, further concentrated microalgae cell, or realize the flushing (removing the impurity such as nutritive salt) of cell of gathering, can be formed directly in more dry algae mud from the good microalgae cell of settling property, can be directly used in the exploitation of derived product, poor or the slightly poor cell from effect of settling, can be by centrifugal, the methods such as filtration are further concentrated, then proceed to the utilization and exploitation of derived product.
The present invention taking resistance to high-alkali, optimum growh pH value scope as 8.2≤pH≤12.3, taking bicarbonate ion as main carbon source and the algae strain of the good pH drift characteristic of the tool algae kind of cultivating as micro-algae large-scale.Such algae kind, in culturing process, is often utilized 1 carbanion, will discharge an OH
-, thereby make culture pH progressively increase, grow faster, pH rises faster, biomass accumulation is more, pH value is higher, when the pH drift causing due to the photosynthetic growth of microalgae cell when culture makes culture pH value exceed 8.2-9.5 scope, in culture, supplement continuously or intermittently carbonic acid gas, make the pH of culture be stabilized in the optimum range between 8.2 ~ 9.5, when reaching suitable, cell concn gathers after concentration, stop supplementing carbonic acid gas, make the pH value of culture increase under the driving of photosynthetic carbon fixation effect, and stop stirring, in the time of pH10.0 ~ 12.3, microalgae cell occurs from sedimentation, after most of microalgae cell in culture sinks to concentrating, collect high-alkali supernatant liquor, the microalgae cell of bottom sedimentation concentration can further obtain algae mud from sedimentation or by centrifugal concentrating.For the algal species cultivation thing of pH drift amplitude not high enough (pH9-9.5), supplement a small amount of alkali lye (as NaOH, solution such as KOH) and can reach the requirement (pH10-10.5) of cell from sedimentation.According to carbonate chemistry equilibrium principle in water body, if after the arbitrary condition in equilibrium system changes, balance just moves to the direction of these changes of weakening.And when passing into CO in the high-alkali supernatant liquor obtaining to separation
2time, CO in supernatant liquor
2the rising of concentration will cause carbonate eqrilibrium system to reducing CO in solution
2the direction of concentration is carried out, and pH value of solution declines, but because acidifying terminal pH is the pH scope (pH>=8.2) of the suitable growth of algae kind, and within the scope of this pH, dissolve in CO in substratum
2mainly with HCO
3 -form exists, and has both been conducive to the cultivation of micro-algae, can prevent again the CO that too low pH causes
2escape leakage, therefore, the CO of 98-100%
2be present in substratum with the form of bicarbonate ion, be equivalent to refill the carbon source that growth consumes in substratum.Therefore, this invention based on resistance to high-alkali algae kind, utilize its pH drift mechanism, significantly reduce or avoided improving in bibliographical information the required alkali lye of pH and added, supplement and the control of acidifying pH terminal by carbonic acid gas, avoid dissolving in the escape of carbonic acid gas, the culture physico chemical factor supplementing after carbonic acid gas (acidification) does not significantly change, substratum can recycle for a long time, effectively avoid chemical flocculation gather the brought inhibition to frustule or murder by poisoning, be difficult to recycle and the problem such as the serious environmental safety that derived.
Therefore the present invention utilizes high pH induction microalgae cell from sedimentation, and efficient concentration frustule, realizes high efficiency, low cost and gather; Coupling CO
2the benefit carbon technique reducing discharging, utilizes the high-alkali supernatant liquor efficient absorption sour gas CO after gathering
2, make the pH of high-alkali supernatant liquor be reduced to the level (pH>=8.2) that is applicable to micro algae growth, realize the efficient benefit carbon of substratum, ensure the recycle of supernatant liquor after gathering, greatly reduce gather cost and fertilizer cost in micro-algae large-scale farming.
Embodiment:
Following examples are to further illustrate of the present invention, instead of limitation of the present invention.
Basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain in following examples, its optimum growh pH value scope be 8.2≤pH≤12.3, adapt to high alkalinity, with HCO
3 -for main carbon source the good pH drift characteristic of tool, using it as algae kind.
Embodiment 1:
Basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain comes from Chinese Academy of Science Nanhai Ocean Research Institute, and using it as algae kind, substratum is modified as basis taking ZSNT, NaHCO
3be revised as 5gL
-1, other are identical, and substratum Initial pH is 8.2.Add 2L substratum with 3L triangular flask, inoculate algae kind, postvaccinal culture OD
700be 0.2, intensity of illumination is 100 μ Em
-2s
-1, 25 DEG C of culture temperature, periodicity of illumination is 14h:10h(light: dark).Under light conditions, shook up once every 4 hours, and detect algae liquid pH, if pH reaches 9.5-10, pass into CO
2substratum is transferred to after pH8.2-8.5, is stopped supplementing CO
2, so repeatedly, the pH value of controlling substratum is between 8.2 ~ 9.5.Algae liquid is cultivated 7 days, and frustule concentration reaches horizontal 0.8g/L to be gathered, and stops supplementing CO
2, no longer controlled the pH of algae liquid, pH in culture medium raises gradually, and frustule starts sedimentation, after sedimentation in 12 hours, frond rate of descent reaches 95%(100% and deducts frond per-cent residual in supernatant liquor).Subsequently supernatant liquor is transferred to another triangular flask by the mode of toppling over, will be collected in centrifuge tube at the frustule of bottom, centrifugal (5000rpm, 10min) further concentrates, and collects and obtains algae mud.The high-alkali supernatant liquor separating is carried out to carbonic acid gas and supplement, pH is reduced to suitable level (pH8.2), supplement 0.4gL simultaneously
-naNO
3, supplementing carbonic acid gas and NaNO subsequently
3inoculation of medium algae liquid, culture OD
700be 0.2, cultivate according to above-mentioned culture condition, substratum recycle.
Compared with traditional centrifugal percentage recovery, the present embodiment has been saved the cost of gathering of about 20 times by high pH induction percentage recovery.
Embodiment 2
Basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 strain comes from Chinese Academy of Science Nanhai Ocean Research Institute, and using it as algae kind, substratum is modified as basis taking ZSNT, and NaHCO3 is revised as 5gL
-1, substratum Initial pH is 8.2.Add 9.6L substratum with 20L glass jar reactor, in 9.6L substratum, access 6.4L basophilic Chlorococcum (Chlorococcum alkaliphilus) MC-1 algae liquid (by the culture medium culturing of the present embodiment), postvaccinal culture OD
700be 0.3, outdoor natural light is cultivated.Under light conditions, stirred once every 4 hours, and detect algae liquid pH, if pH reaches 9.5-10, pass into CO
2substratum is transferred to after pH8.2-9, is stopped supplementing CO
2, so repeatedly, the pH value of controlling substratum is between 8.2 ~ 9.5.Algae liquid is cultivated 3 days, and frustule concentration reaches horizontal 1g/L to be gathered, and stops supplementing CO
2, no longer controlled the pH of algae liquid, pH in culture medium raises gradually, and frustule starts sedimentation, takes out 6 liters of algae liquid in the container of gathering, after sedimentation overnight, frond rate of descent reaches 98%(100% and deducts frustule per-cent residual in supernatant liquor).Supernatant liquor was shifted to another container of gathering in second day, the frustule that is deposited in bottom is collected, further, after natural subsidence, collect the algae mud (8% dry weight) highly being concentrated.The high-alkali supernatant liquor separating is carried out to carbonic acid gas and supplement, pH is reduced to suitable level (pH8.2), supplement 0.4gL simultaneously
-naNO
3with a small amount of phosphorus, ferro element, will add NaNO
3proceed in the incubator of not gathering with the substratum of a small amount of phosphorus, ferro element, cultivate according to above-mentioned culture condition, realize substratum recycle.
In sun-drenched situation, after gathering, can gather again every 2 days, Cyclic culture-gathering-substratum this process that circulates, has realized the semicontinuous cultivation of 2 months and has gathered.The present embodiment, compared with traditional centrifugal percentage recovery, has been saved the cost of gathering of about 22 times by high pH induction percentage recovery.
Claims (1)
1. micro-algae of high pH induction, coupling carbon dioxide discharge-reduction novel method of gathering, is characterized in that, selects optimum growh pH value in 8.2≤pH≤12.3 scope, adaptation high alkalinity, with HCO
3 -for micro-algae of main carbon source the good pH drift characteristic of tool is as algae kind, it is carried out to cellar culture with the substratum of micro-algae, the inorganic carbon source in described substratum is with HCO
3 -be main, CO is used in initial pH>=8.2 of substratum in culturing process
2the pH value of controlling culture system is between 8.2～9.5, gathers after concentration when microalgae density reaches suitable, stops supplementing CO
2no longer control the pH value of culture system, under the driving of microalgae cell photosynthetic carbon fixation effect, make the pH value of culture rise between pH10～12.3, induction microalgae cell is from sedimentation, microalgae cell precipitation concentrates in bottom of culture vessel, upper strata nutrient solution is progressively clarified, lower floor's microalgae cell precipitation is separated with the high-alkali supernatant liquor in upper strata, the microalgae cell being precipitated thus and high-alkali supernatant liquor, then fill into CO in high-alkali supernatant liquor
2its pH value is reduced to the pH value level of suitable micro algae growth, supplements because microalgae cell is grown other nutritive substances of consuming and carries out recycle as new substratum and cultivate micro-algae simultaneously;
Described algae kind be basophilic Chlorococcum (
chlorococcum alkaliphilus) MC-1 strain;
Described substratum is improvement ZSNT substratum, its NaHCO
3for 5g/L, other are identical with ZSNT medium component.
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