CN111560317A - Application of novel surfactant in microalgae froth flotation harvesting - Google Patents

Application of novel surfactant in microalgae froth flotation harvesting Download PDF

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CN111560317A
CN111560317A CN202010374540.1A CN202010374540A CN111560317A CN 111560317 A CN111560317 A CN 111560317A CN 202010374540 A CN202010374540 A CN 202010374540A CN 111560317 A CN111560317 A CN 111560317A
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microalgae
flotation
novel surfactant
recovery
collector
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CN111560317B (en
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黄志强
余新阳
邱廷省
何桂春
李立清
刘汝宽
罗武辉
成晨
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Jiangxi University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/02Separating microorganisms from their culture media
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/012Organic compounds containing sulfur
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/02Collectors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/001Agricultural products, food, biogas, algae
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/003Biotechnological applications, e.g. separation or purification of enzymes, hormones, vitamins, viruses
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/02Ores

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Abstract

The invention discloses application of a novel surfactant in microalgae froth flotation and recovery, wherein the novel surfactant shown as a formula I is used as a flotation collector in the microalgae froth flotation and recovery. The novel surfactant is used as a flotation collector for microalgae froth flotation recovery, the molecular structure of the novel surfactant contains two hydrophobic groups and a plurality of hydrophilic groups, the hydrophobic capability of the collector is improved due to the existence of double hydrophobic tail chains, and the adsorption of molecules of the collector on the surfaces of microalgae can be promoted due to the existence of multiple hydrophilic head groups, so that the flotation performance of the collector on the microalgae is enhanced; compared with the collecting agent used in the existing microalgae froth flotation recovery technology, the collecting efficiency and the recovery rate can be obviously improved.

Description

Application of novel surfactant in microalgae froth flotation harvesting
Technical Field
The invention belongs to the technical field of mineral separation, and particularly relates to application of a novel surfactant in microalgae froth flotation and harvesting.
Background
At present, the rapid development in China is seriously faced with the problem of energy shortage caused by industrialization and urbanization. The microalgae biodiesel is obtained by converting microalgae into hydrocarbon substances through physiological regulation, or directly extracting oil from the microalgae by a high-temperature high-pressure liquefaction method, reacting to obtain fatty acid methyl ester with small relative molecular mass, and finally washing and drying (plant science bulletin 2008, 26 (6): 650-. The microalgae is a renewable biological energy source raw material, has the characteristics of short growth cycle, strong adaptability, good salt resistance, oil content accounting for 60-70% of the dry weight of cells and the like, and is suitable for large-scale industrial culture (new energy development, 2018, 6 (6): 467-.
However, the existing research mainly focuses on the culture of microalgae, and few researches relate to the aspect of algae harvesting. According to data statistics, the energy consumption of the equipment for microalgae recovery and enrichment accounts for 30% of the whole industrial production (Bioresource technology, 2018, 269: 188-. Shenying, etc. have reviewed the main technical means currently used for microalgae harvesting and enrichment, namely settling, filtration, centrifugation, flocculation and flotation (Hubei agricultural science, 2012, 51 (22): 4982-. Flotation is a technical means which is widely applied in the fields of mineral separation, wastewater treatment and the like at present, but is not applied to the harvesting link of microalgae in a mature way at present.
Thea Coward et al, using cetyltrimethylammonium bromide (see formula a) as a collector, demonstrated that flotation was indeed more efficient than the centrifugation methods currently used in industrial production (Biomass and Bioenergy, 2014, (67): 354:. 362). Chen Y.M. and the like compare two collectors, namely a cationic collector Cetyl Trimethyl Ammonium Bromide (CTAB) and an anionic collector sodium dodecyl sulfate (SDS, shown in a structural formula b), and the results show that the recovery rate of SDS to algae is about 10 percent, and the recovery rate of CTAB to algae can reach more than 90 percent; when SDS is used as a collecting agent, 10mg/L of chitosan is added, and the algae removal rate can reach 90% (Colloids and Surfaces B: Biointerfaces, 1998, 12: 49-55). Zhang Haiyang and the like take dodecylamine (shown as a structural formula c) as a collecting agent, and the influence of the using amount of the collecting agent, the stirring rotation speed, the concentration of algae liquid, the pH value of the solution and the flotation time on the chlorella harvesting efficiency is researched by utilizing an orthogonal experiment, and the result shows that the optimal conditions for harvesting the chlorella are that the using amount of the dodecylamine is 30mg/L, the stirring rotation speed is 1200r/min and the flotation time is 3min, and the recovery rate can reach 98.35% (renewable energy, 2016, 34 (2): 268 and 273). Patent CN201710712868.8, "a porphyridium harvesting method based on froth flotation", discloses a method for collecting floating products by froth flotation by using rhamnolipid (see structural formula d) in combination with foaming agent. At present, the collecting agent used in the foam flotation and recovery of microalgae is a traditional surfactant with a single hydrophobic group and a single hydrophilic group, and has the defects of poor selectivity, large using amount and weak collecting capability. Therefore, in order to solve the technical problem of poor flotation index in the current microalgae froth flotation and recovery, the novel efficient microalgae froth flotation collector with strong collecting capacity and good selectivity is researched and developed, and the method has great significance for the development and utilization of microalgae resources and the sustainable development of agriculture and related industries. The present invention has been made in view of this situation.
Figure BDA0002479465930000021
(structural formula a: hexadecyltrimethylammonium bromide)
Figure BDA0002479465930000022
(structural formula b: sodium dodecyl sulfate)
CH3(CH2)10CH2NH2(structural formula c: dodecyl Primary amine)
Figure BDA0002479465930000023
(structural formula d: rhamnolipid)
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a novel surfactant for recovering microalgae by froth flotation as a flotation collector, and solves the problems of poor recovery rate, low enrichment ratio and high recovery cost of microalgae in the process of microalgae froth flotation recovery caused by poor selectivity, large using amount and weak collecting capability of the traditional surfactant with a single hydrophobic group and a single hydrophilic group in the process of microalgae froth flotation recovery.
In order to solve the technical problems, the invention adopts the technical scheme that:
the application of the novel surfactant in microalgae froth flotation recovery uses the novel surfactant shown as a formula I as a flotation collector in the microalgae froth flotation recovery, and the novel surfactant has the structure shown as the formula I:
Figure BDA0002479465930000031
the novel surfactant shown as the formula I is used as a flotation collector in microalgae foam flotation and collection, the pH value range of microalgae flotation liquid is 7-10, and the algae cell density of the algae liquid is 1 × 108cells/L~6×108The dosage of the novel surfactant is 10-40 mg/L, and the microalgae is specifically one of chlorella, porphyridium and scenedesmus obliquus.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
(1) The molecules of the flotation collector of the novel surfactant have a plurality of hydrophilic groups, the action capacity with the surface of microalgae is stronger, the selectivity to the microalgae is better, the adsorption of the collector molecules on the surface of algae cells can be promoted, and the flotation enrichment ratio can be improved;
(2) the molecule of the collecting agent has two hydrophobic groups, so that the hydrophobic capacity of the collecting agent is improved, the collecting capacity of the collecting agent on microalgae is stronger, and the flotation effect of the microalgae can be enhanced;
(3) the flotation collecting agent of the novel surfactant has strong collecting capacity and good selectivity on microalgae, improves the gathering ratio and recovery rate of microalgae harvesting, solves the technical problems of large using amount of the collecting agent and low gathering ratio and recovery rate of the microalgae in the traditional surfactant, and has good popularization and application values.
The following describes in further detail embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not used for limiting the scope of the present invention.
The invention provides a novel surfactant for microalgae froth flotation recovery, which has a structure shown in a formula I:
Figure BDA0002479465930000032
example 1
The cell density of the chlorella solution to be collected is 1.9344 × 108cell/L, the pH value of the algae liquid is 9, 35mL of the algae liquid is transferred to a flotation machine and then stirred for 2min, the novel surfactant shown as the formula I is added into the flotation machine at the flotation concentration of 15mg/L, the mixture is stirred for 2min at the rotating speed of 2000rpm, the flotation is stopped after 3min, after the algae mud is removed, the tailings are weighed, and the cell density is measured by a spectrophotometry method. The calculated recovery rate of the chlorella is 99.21 percent, and the enrichment ratio is 25.
Example 2
The cell density of the chlorella solution to be collected is 5.1793 × 108cells/L, the pH of the algae solution is 7, and 1500mL of algae solution is transferred toTransferring to a flotation machine, stirring for 3min, adding a novel surfactant shown as formula I or a common collecting agent cetyl trimethyl ammonium bromide into the flotation machine at a flotation concentration of 30mg/L, stirring at 2000rpm for 3min, stopping after 10min of flotation, weighing tailings after algae mud is removed, and measuring the cell density by spectrophotometry. Calculating to obtain the recovery rate of the chlorella to be 99.86% and the enrichment ratio to be 21 when the novel surfactant shown as the formula I is adopted; when the common collecting agent cetyl trimethyl ammonium bromide is adopted, the recovery rate of the chlorella is 45.17 percent, and the enrichment ratio is 7. Compared with a common collecting agent cetyl trimethyl ammonium bromide, when the novel surfactant shown as the formula I is used, the recovery rate of the chlorella is improved by 54.69 percentage points, and the enrichment ratio is improved by 14 percentage points.
Example 3
The cell density of the porphyridium liquid to be collected is 3.0572 × 108cells/L, the pH value of the algae liquid is 10, 1000mL of the algae liquid is transferred to a flotation machine and then stirred for 4min, a novel surfactant shown as a formula I is added into the flotation machine at the flotation concentration of 40mg/L, the mixture is stirred for 4min at the rotating speed of 2000rpm, the flotation is stopped after 8min, after the algae mud is removed, the tailings are weighed, and the cell density is measured by a spectrophotometry method. The calculated recovery rate of the porphyridium is 95.53 percent, and the enrichment ratio is 18.
Example 4
The cell density of the porphyridium liquid to be collected is 1.0554 × 108The method comprises the steps of (1) transferring 750mL of algae liquid to a flotation machine, stirring for 3min, adding a novel surfactant shown as a formula I or a common collecting agent dodecylamine into the flotation machine at the flotation concentration of 35mg/L, stirring for 3min at the rotation speed of 2000rpm, stopping after 9min of flotation, weighing tailings after algae mud is removed, and measuring the cell density by a spectrophotometry. Calculating to obtain the recovery rate of the porphyridium as 92.64% and the enrichment ratio of 23 when the novel surfactant shown as the formula I is adopted; when the common collecting agent of the dodecylamine is adopted, the recovery rate of the porphyridium is 58.93 percent, and the enrichment ratio is 6. Compared with the common collecting agent dodecylamine, when the novel surfactant shown as the formula I is used, the recovery rate of the porphyridium is improved by 33.71 percentage points, and the enrichment ratio is improved by 17And (4) percentage points.
Example 5
The cell density of Scenedesmus obliquus solution to be collected is 4.4472 × 108The method comprises the steps of (1) transferring 500mL of algae liquid into a flotation machine, stirring for 3min, adding a novel surfactant shown as a formula I into the flotation machine at a flotation concentration of 20mg/L, stirring for 3min at a rotating speed of 2000rpm, stopping after 6min of flotation, weighing tailings after algae mud is removed, and measuring the cell density through a spectrophotometry, wherein the pH of the algae liquid is 8. The calculated recovery rate of Scenedesmus obliquus is 97.53%, and the enrichment ratio is 22.
Example 6
The cell density of Scenedesmus obliquus solution to be collected is 1.0317 × 108cell/L, the pH value of the algae liquid is 10, 3000mL of the algae liquid is transferred to a flotation machine and then stirred for 3min, a novel surfactant shown as a formula I or a common collecting agent cetyl trimethyl ammonium bromide is added into the flotation machine at the flotation concentration of 16mg/L, the mixture is stirred for 3min at the rotating speed of 2000rpm, the flotation is stopped after 9min, after algae mud is removed, tailings are weighed, and the cell density is measured by a spectrophotometry method. Calculating to obtain the recovery rate of scenedesmus obliquus of 98.42% and the enrichment ratio of 26 when the novel surfactant shown as the formula I is adopted; when the common collecting agent cetyl trimethyl ammonium bromide is adopted, the recovery rate of scenedesmus obliquus is 52.86%, and the enrichment ratio is 9. Compared with a common collecting agent cetyl trimethyl ammonium bromide, when the novel surfactant shown as the formula I is used, the recovery rate of Scenedesmus obliquus is improved by 45.56 percentage points, and the enrichment ratio is improved by 17 percentage points.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (1)

1. The application of the novel surfactant in microalgae froth flotation recovery is characterized in that the novel surfactant shown as the formula I is used as a flotation collector in the microalgae froth flotation recovery, the pH value range of a microalgae flotation solution is 7-10, the algae cell density of the algae solution is 1 × 108cells/L~6×108cells/L, wherein the dosage of the novel surfactant is 10-40 mg/L, and the microalgae is specifically one of chlorella, porphyridium and scenedesmus obliquus;
Figure FDA0002479465920000011
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112495577A (en) * 2020-12-28 2021-03-16 海南文盛新材料科技有限公司 Ore dressing process for separating zirconite by using grading jigger

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Publication number Priority date Publication date Assignee Title
CN112495577A (en) * 2020-12-28 2021-03-16 海南文盛新材料科技有限公司 Ore dressing process for separating zirconite by using grading jigger

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