CN110160916A - A kind of experimental method for the carrier material screening efficient absorption microalgae - Google Patents

A kind of experimental method for the carrier material screening efficient absorption microalgae Download PDF

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CN110160916A
CN110160916A CN201810182025.6A CN201810182025A CN110160916A CN 110160916 A CN110160916 A CN 110160916A CN 201810182025 A CN201810182025 A CN 201810182025A CN 110160916 A CN110160916 A CN 110160916A
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microalgae
carrier material
formula
algae
free energy
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崔岩
成家杨
袁文桥
李静
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02—Investigating surface tension of liquids
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02—Investigating surface tension of liquids
    • G01N2013/0208—Investigating surface tension of liquids by measuring contact angle

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
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Abstract

The present invention is based on thermodynamical models, the mechanism of action between microalgae and adsorption carrier material is had studied from energy variation angle, sum up a kind of experimental method of carrier material for screening efficient absorption microalgae, to improve microalgae in the absorption of surfaces of carrier materials and the formation of biomembrane, and then it is applied to the biological treatment of industrial wastewater and sanitary sewage.The present invention passes through preparation microalgae algae film, and then the surface property of microalgae and carrier material is measured, finally by the building of thermodynamical model, the suction-operated between microalgae and carrier material is calculated and predicted from molecular level, and there is certain theory and practice directive significance to the development and application of the processing of microalgae biological sewage.

Description

A kind of experimental method for the carrier material screening efficient absorption microalgae
Technical field
The invention belongs to material science and environmental science, and in particular to a kind of carrier material for screening efficient absorption microalgae The experimental method of material.
Background technique
Microalgae is considered playing an important role in the self purification process of natural water body, early in the 1950s, just having Person proposes the imagination using microalgae processing sewage.It hereafter, is the suspension growth system of representative in distributing dirt using High-Rate Algae Pond Extensive engineer application is obtained in water process, but this kind of suspension system has the offices such as take up a large area, treatment effect is unstable It is sex-limited.Immobilized microorganism technique, which refers to be fixed on free microorganism with physically or chemically means, to be limited space and keeps Its activity is subject to a kind of technology of Reusability, is used primarily for the fixation of biological enzyme, by the development of many years, is also widely used for The culture and breeding of the microbial cells such as bacterium, yeast.Immobilization technology microalgae field application start from the 1980s, Correlative study mainly includes the culture of cell and the biological treatment of sewage.Compared with conventional suspension formula culture, Immobilized culture tool The advantages that having convenient for biomass collection, reduce culture expense, improving microalgae cell film yield and then improve waste water treatment efficiency.Have The new Alga technology for closing Immobilized culture mode just has become a hot topic of research.
Based on the active principle of microalgae cell is not influenced, investment and absorption method are two kinds of main microalgae immobilizations at present Method.Investment is trapped in microalgae cell in the cyberspace of gel complex compound of water-insoluble, and the method is complicated for operation And it is at high cost, thus limit its large-scale practical application.Though there are the limits of cell fixed number and fixing intensity for absorption method System, but with the progress of material technology, the performance for improving absorption can be improved by the characteristic to material surface, and This method has easy to operate, low in cost, the advantages that cell easily recycles, therefore relatively simple absorption method is increasingly becoming fixation Change the development trend of microdisk electrode.But during adsorption of immobilization, adsorption effect difference of the different algal species on different carriers It is larger.Common carrier material includes that high-molecular organic material (fiber, nylon, plastics etc.), inorganic carrier are (kaolinite, porous Porcelain, cellular glass etc.) and metal material (stainless steel, iron, titanium etc.).However in practical applications, it is difficult through complexity Experiment is to be matched and be verified one by one to the adsorption between microalgae and numerous carrier materials.The present invention utilizes thermodynamics mould Type, the algae of corresponding every kind of sewage treatment, can quickly filter out the matching material with best absorption property, thus real Maximum adhesion of the existing frustule in the surfaces of carrier materials.
Studies have shown that the suction-operated of microalgae cell and carrier depends primarily on the interaction force between cell and carrier, The physicochemical properties of the size of this active force and microalgae surface and carrier material have substantial connection.In thermodynamics field, These physicochemical properties can be characterized by some surface thermodynamics parameters, including the Van der Waals component in surface tension (γLW), lewis acid alkaline constituents (γAB) electron donor (γ-) and electron acceptor (γ+).By the measurements of these parameters or It calculates, microalgae can be obtained and become in surfaces of carrier materials adsorption free energy, disclose the heating power to interact between microalgae and carrier material Essence is learned, to filter out the material for being more advantageous to microalgae absorption.Currently, surface nature and microalgae cell about carrier material Association between adsorption effect does not carry out system research also.
Summary of the invention
The present invention is intended to provide a kind of carrier material for screening efficient absorption microalgae.Above-mentioned mesh to realize the present invention , used technical solution is:
A kind of experimental method for the carrier material screening efficient absorption microalgae, includes the following steps,
1. microalgae algae film is prepared,
By the microalgae cell of culture to logarithmic phase latter stage, with acetate fiber filter membrane (≤0.45 μm) to algae solution (106/ mL) into Row takes out filtration membrane, enables it form thick 200 μm -250 μm of algae film on filter membrane, is air-dried at room temperature, obtains stablizing microalgae algae film；
2. 1. algae film and the separately sampled product of clean carrier material that step obtains is placed in contact angle measurement, use Microsyringe will test liquid and be respectively perpendicular drop in algae membrane sample and carrier material sample surfaces, stand detection liquid drop The contact angle that microalgae cell sample and carrier material sample surfaces are measured after 20s, carries out Contact-angle measurement；
3. using the Lifshitz-van der Waals/acid-base approach (LW-AB) based on contact angle method Method calculates the surface energy parameter of frustule and carrier material, and the calculation is described below,
Total surface energy is represented with γ, then can be divided into two parts, such as formula (1):
γ=γLW+γAB (1)
γLWIt is nonpolar moiety for Lifshitz-van derWaals component；γABIt is polar portion, and includes Lewis acid component γ+With Lewis alkali component γ-, relationship such as formula (2):
Formula is handled, the interactively such as formula (3) of two-phase is obtained:
By Young equation γS-γSL=γLcosθ(γS、γSL、γLRespectively indicate solid, solid-liquid, liquid surface from By energy；θ is contact angle) and formula (3) combine then obtain formula (4):
Liquid can be detected known to parameters using three kinds of surfaces, measure their connecing in algae film and surfaces of carrier materials respectively Feeler θ, each surface that microalgae and carrier material can be calculated according to formula (4) can parameter.
4. using step 3. obtained in microalgae and carrier material surface can parameter, be calculated by thermodynamical model The energy variation of adsorption process, by model prediction microalgae cell surfaces of carrier materials adsorption effect,
Calculation and prediction principle are illustrated as follows:
The process that microalgae is adsorbed on carrier surface can cause the free energy on interact two surfaces to change, It is expressed as follows by Thermodynamics Formulas:
ΔGadh=γms-γml-γsl (5)
ΔGadhIt is adsorption free energy；γmsIt is the interfacial free energy between carrier material and microalgae；γmlIt is microalgae and liquid Interfacial free energy between body；γslIt is the interfacial free energy between carrier material and liquid.ΔGadhAlso consist of two parts,WithSuch as formula (6):
Wherein,
According to formula (6)-(8), in conjunction with step 3. obtained in surface can parameter, microalgae and carrier material phase is calculated The adsorption free energy of interacting system changes (Δ Gadh).The variation of the free energy is smaller, the absorption between microalgae and carrier material It is more easy to happen, thus predicts microalgae cell in the absorption result of different carriers material surface.
Further, a kind of experimental method for the carrier material screening efficient absorption microalgae, the microalgae include but not It is limited to scenedesmus, micro- quasi- ball algae, Wild Vitis species, chlorella, Phaeodactylum tricornutum, Dunaliella salina, the carrier material includes but unlimited In high-molecular organic material and metal material.
Further, it is a kind of screen efficient absorption microalgae carrier material experimental method, step 2. in for guarantee contact 15 seats drop contacts are obtained in the reproducibility at angle, algae film and the equal duplicate measurements of carrier material 3 times, 5 seats drops of each random measurement Angle is averaged the contact angle as the detection liquid in sample surfaces.
Detailed description of the invention
Fig. 1 is adsorption density schematic diagram of the chlorella in 6 kinds of surfaces of carrier materials；
Fig. 2 is adsorption density schematic diagram of the scenedesmus in 6 kinds of surfaces of carrier materials.
Specific embodiment
To illustrate the invention, further detailed description is done to the present invention below with reference to the example of specific implementation, but originally The protection scope of invention is not limited to following embodiment.Improvements introduced and modification on the basis of the present invention belong to the present invention and want The protection scope asked.
Specific embodiment 1: the present invention relates to suction-operated research is carried out with chlorella and 6 kinds of carrier materials, from 6 kinds of materials In filter out the carrier material of suitable chlorella absorption.
The present invention carries out suction-operated research with chlorella and 6 kinds of materials, through the following steps that realize:
1, chlorella algae film: the chlorella in logarithmic growth phase latter stage is prepared, by algae solution (1.0 × 106/ mL) with 0.45 μm Acetate fiber filter membrane suction filtration processing, after its surface formed 200 μ m-thicks algae film after, be air-dried at room temperature processing it is spare；
2, the Contact-angle measurement and surface of microalgae and carrier material can calculate: material cleans 20min in supersonic cleaning machine, 5min is rinsed with deionized water again, is air-dried at room temperature.The algae film that step 1 obtains is placed in contact angle measurement with the material cleaned In the contact angle of algae film surface and material surface is measured.Detection liquid is hung down by the 1mL microsyringe of measuring instrument Straight drippage is in the surface of each sample, and detecting liquid product is 3 μ L, and after about 20 seconds, drop is in stable state and carries out contact angle again Measurement.To ensure the accuracy tested, three Duplicate Samples are all arranged in algae film and all material.It is taken in three parallel samples Contact-angle measurement is carried out at 5, and the average value of 15 measurement results is finally taken to be determined as the detection liquid in the contact of kind of sample surfaces Angular data, the above measurement all carry out (25 DEG C) at room temperature.
Research utilizes the LW-AB method based on contact angle method, and the various heat of algae film and material surface are calculated by formula Mechanics parameter and surface energy.Total surface energy is represented with γ, then can be divided into two parts, such as formula (1):
γ=γLW+γAB (1)
γLWIt is nonpolar moiety for Lifshitz-van derWaals component；γABIt is polar portion, and includes Lewis acid component γ+With Lewis alkali component γ-, relationship such as formula (2):
Formula is handled, the interactively such as formula (3) of two-phase is obtained:
By Young equation γS-γSL=γLcosθ(γS、γSL、γLRespectively indicate solid, solid-liquid, liquid surface from By energy；θ is contact angle) and formula (3) combine then obtain formula (4):
To obtain required each Wahburn, liquid known to tri- kinds of surface parameters of Yao Liyong measures them in solid The contact angle θ on surface, each surface that chlorella and carrier material can be acquired according to formula (4) can parameter.Using deionized water, For three kinds of reagents of diiodomethane and formamide as detection liquid, the surface of three kinds of liquid can parameter such as table 1.
Table 1 detects liquid surface can parameter (mJm-2)
It is measured obtained contact angular data and is shown in Table 2.Via the table of chlorella and carrier material that formula (4) is calculated Face performance parameter is shown in Table 2.
The contact angle and surface of 2 chlorella of table and carrier material can parameters
Note: contact angle error is ± 5 °
3, establish thermodynamical model: the process that microalgae is adsorbed on carrier surface can cause interact two surfaces Free energy change, be expressed as follows by Thermodynamics Formulas:
ΔGadh=γms-γml-γsl (5)
ΔGadhIt is adsorption free energy；γmsIt is the interfacial free energy between carrier material and microalgae；γmlIt is microalgae and liquid Interfacial free energy between body；γslIt is the interfacial free energy between carrier material and liquid.ΔGadhAlso consist of two parts,WithSuch as formula (6):
Wherein,
Chlorella and carrier material interface phase interaction is calculated in conjunction with the data that table 2 obtains according to formula (6)-(8) It is as shown in table 3 with free energy.
Interfacial interaction free energy (mJm between 3 chlorella of table and carrier material-2)
As shown in Table 3, chlorella is both less than zero with total adsorption free energy of 6 kinds of materials, i.e., chlorella is in 6 kinds of material surfaces Suction-operated can occur.The smallest adsorption free energy is nylon, is -25.24mJm-2, show the material to chlorella Suction-operated is best.Adsorption effect it is worst should be titanium, adsorption free energy is -2.32mJm-2.Wherein,For positive value, Repulsive interaction is shown as, is had a negative impact to the absorption of chlorella.
4, the absorption property of chlorella and material is tested: culture to the chlorella suspension in logarithmic phase latter stage and 6 kinds are carried Body material, which is collectively disposed in the beaker of dark place, carries out absorption test, for 24 hours afterwards takes out carrier material with tweezers, in deionized water Then light drift uses fluorescence to cell dyeing with 0.1% acridine orange stain to remove the unstable microalgae cell of adsorption Optical microscopy (Olympus BX-53) is taken pictures in random 5 positions and is counted to microalgae cell.According to cell counts, meter The total number of cells that microalgae is adsorbed on a support material are calculated, total number of cells can calculate every square divided by the area of carrier material The frustule of centimetre carrier material adsorbs quantity.Above procedure is completed under static conditions and room temperature (25 DEG C).Chlorella exists The attachment the result is shown in Figure 1 of each surfaces of carrier materials.Adsorption density of the chlorella on nylon surface reaches 6.0x105/cm2, phase therewith Pair hydrophobicity difference surface can high titanium adsorption density be only 2.5x105/cm2.By in the thermodynamical model of step 3 it is found that The lesser material of adsorption free energy is more advantageous to the attachment of frustule, consistent with experimental result in this step, demonstrates model sieve The correctness of choosing.
Specific embodiment 2: the present invention relates to carrying out suction-operated research with scenedesmus and 6 kinds of carrier materials, from 6 kinds of materials Filter out the carrier material of suitable scenedesmus absorption.
Present invention scenedesmus and 6 kinds of materials carry out suction-operated research, through the following steps that realize:
1, scenedesmus algae film: the scenedesmus in logarithmic growth phase latter stage is prepared, by algae solution (1.0 × 106/ mL) with 0.45 μm of vinegar It is spare to be air-dried at room temperature processing after its surface forms the algae film of 200 μ m-thicks for sour fibrous filter membrane suction filtration processing；
2, the Contact-angle measurement and surface of scenedesmus and carrier material can calculate: material cleans 20min in supersonic cleaning machine, 5min is rinsed with deionized water again, is air-dried at room temperature.Algae film that step 1 obtains and clean material are placed in contact angle measurement The contact angle of algae film surface and material surface is measured.Detection liquid is vertically dripped by the 1mL microsyringe of measuring instrument The surface of each sample is fallen within, detection liquid product is 3 μ L, and after about 20 seconds, drop is in stable state, and this carries out contact angle again Measurement.To ensure the parasexuality tested, three Duplicate Samples are all arranged in algae film and all material.It is taken at 5 in three parallel samples Contact-angle measurement is carried out, the average value of 15 measurement results is finally taken to be determined as the detection liquid in the contact angle number of kind of sample surfaces According to the above measurement all carries out (25 DEG C) at room temperature.
Research utilizes the LW-AB method based on contact angle method, and the various heating power of scenedesmus and material surface are calculated by formula Learn parameter and surface energy.Liquid known to three kinds of surface parameters is shown in Table 1, through the contact angle for measuring obtained scenedesmus and 6 kinds of materials Data are shown in Table 4.The surface energy parameter for the scenedesmus and 6 kinds of materials being calculated via formula (4) is shown in Table 4.
The contact angle and surface of 4 scenedesmus of table and carrier material can parameters
Note: contact angle error is ± 5 °
3, establish thermodynamical model: the process that microalgae is adsorbed on surfaces of carrier materials can cause interact two The free energy on surface changes, and scenedesmus and 6 is calculated in conjunction with the data that table 4 obtains by Thermodynamics Formulas (5)-(8) Kind carrier material interfacial interaction free energy is as shown in table 5.
Interfacial interaction free energy (mJm between 5 scenedesmus of table and carrier material-2)
As shown in Table 5, scenedesmus is both less than zero with total adsorption free energy of 6 kinds of materials, i.e. suction of the scenedesmus in 6 kinds of material surfaces Attached effect can occur.The smallest adsorption free energy is nylon, is -30.93mJm-2, show absorption of the material to chlorella Effect is best.Adsorption effect it is worst should be titanium, adsorption free energy is -5.37mJm-2。
4, the absorption property of scenedesmus and material is tested: by culture to the scenedesmus suspension in logarithmic phase latter stage and 6 kinds of carrier materials Material, which is collectively disposed in the beaker of dark place, carries out absorption test, for 24 hours afterwards takes out carrier material with tweezers, in deionized water light drift To remove the unstable microalgae cell of adsorption, fluorescent optics then is used to cell dyeing with 0.1% acridine orange stain Microscope (Olympus BX-53) is taken pictures in random 5 positions and is counted to microalgae cell.According to cell counts, calculate The total number of cells that microalgae is adsorbed on a support material, total number of cells can calculate every square centimeter divided by the area of carrier material The frustule of carrier material adsorbs quantity.Above procedure is completed under static conditions and room temperature (25 DEG C).Scenedesmus is in each carrier The attachment result of material surface is shown in Fig. 2.Adsorption density of the scenedesmus on nylon surface reaches 7.3x105/cm2, on the other side hydrophobic Property difference surface can high titanium adsorption density be only 2.9x105/cm2.By in the thermodynamical model of step 3 it is found that absorption freely The lesser material of energy is more advantageous to the attachment of frustule, consistent with experimental result in this step, demonstrates the correct of model discrimination Property.

Claims (3)

1. a kind of experimental method for the carrier material for screening efficient absorption microalgae, it is characterised in that: include the following steps,
1. microalgae algae film is prepared,
By the microalgae cell of culture to logarithmic phase latter stage, with acetate fiber filter membrane (≤0.45 μm) to algae solution (106/ mL) it is taken out Filtration membrane enables it form thick 200 μm -250 μm of algae film on filter membrane, is air-dried at room temperature, obtains stablizing microalgae algae film；
2. 1. algae film and the separately sampled product of clean carrier material that step obtains is placed in contact angle measurement, use is micro Sample injector will test liquid and be respectively perpendicular drop in algae membrane sample and carrier material sample surfaces, after standing detection liquid drop 20s The contact angle of algae membrane sample and carrier material sample surfaces is measured, Contact-angle measurement is carried out；
3. Lifshitz-van der Waals/acid-base approach (LW-AB) method based on contact angle method of using The surface energy parameter of frustule and carrier material is calculated, the calculation is described below,
Total surface energy is represented with γ, then can be divided into two parts, such as formula (1):
γ=γLW+γAB (1)
γLWIt is nonpolar moiety for Lifshitz-van der Waals component；γABIt is polar portion, and includes Lewis acid Component γ+With Lewis alkali component γ-, relationship such as formula (2):
Formula is handled, the interactively such as formula (3) of two-phase is obtained:
By Young equation γS-γSL=γLcosθ(γS、γSL、γLRespectively indicate the surface free energy of solid, solid-liquid, liquid； θ is contact angle) and formula (3) combine then obtain formula (4):
Liquid can be detected known to parameter using three kinds of surfaces, measure them respectively in the contact angle of algae film and surfaces of carrier materials θ, each surface that microalgae and carrier material can be calculated according to formula (4) can parameter.
4. using step 3. obtained in microalgae and carrier material surface can parameter, absorption is calculated by thermodynamical model The energy variation of process, by model prediction microalgae cell surfaces of carrier materials adsorption effect,
Calculation and prediction principle are illustrated as follows:
The process that microalgae is adsorbed on carrier surface can cause the free energy on interact two surfaces to change, and pass through Thermodynamics Formulas is expressed as follows:
ΔGadh=γms-γml-γsl (5)
ΔGadhIt is adsorption free energy；γmsIt is the interfacial free energy between carrier material and microalgae；γmlIt is between microalgae and liquid Interfacial free energy；γslIt is the interfacial free energy between carrier material and liquid.ΔGadhAlso consist of two parts,WithSuch as formula (6):
Wherein,
According to formula (6)-(8), in conjunction with step 3. obtained in surface can parameter, microalgae and carrier material phase interaction is calculated Change (Δ G with the adsorption free energy of systemadh).The variation of the free energy is smaller, and the absorption between microalgae and carrier material is more held Easily occur, thus predicts microalgae cell in the absorption result of different carriers material surface.
2. a kind of experimental method of carrier material for screening efficient absorption microalgae according to claim 1, it is characterised in that: The microalgae includes but is not limited to scenedesmus, micro- quasi- ball algae, Wild Vitis species, chlorella, Phaeodactylum tricornutum, Dunaliella salina, described Carrier material includes but is not limited to high-molecular organic material and metal material.
3. a kind of experimental method of carrier material for screening efficient absorption microalgae according to claim 1, it is characterised in that: Step 2. in for the reproducibility that guarantees contact angle, algae film and the equal duplicate measurements of carrier material 3 times, 5 seats drops of each random measurement, 15 seat drop contact angles are obtained, are averaged the contact angle as the detection liquid in sample surfaces.
CN201810182025.6A 2018-03-06 2018-03-06 A kind of experimental method for the carrier material screening efficient absorption microalgae Pending CN110160916A (en)

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CN201810182025.6A CN110160916A (en) 2018-03-06 2018-03-06 A kind of experimental method for the carrier material screening efficient absorption microalgae

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