CN111560317B - Application of surfactant in microalgae froth flotation recovery - Google Patents
Application of surfactant in microalgae froth flotation recovery Download PDFInfo
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- CN111560317B CN111560317B CN202010374540.1A CN202010374540A CN111560317B CN 111560317 B CN111560317 B CN 111560317B CN 202010374540 A CN202010374540 A CN 202010374540A CN 111560317 B CN111560317 B CN 111560317B
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 23
- 238000009291 froth flotation Methods 0.000 title claims abstract description 20
- 238000005188 flotation Methods 0.000 claims abstract description 43
- 241000195493 Cryptophyta Species 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 21
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 12
- 241000316848 Rhodococcus <scale insect> Species 0.000 claims description 7
- 241000195663 Scenedesmus Species 0.000 claims description 2
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 11
- 238000003306 harvesting Methods 0.000 description 8
- 235000007122 Scenedesmus obliquus Nutrition 0.000 description 6
- 241000195662 Tetradesmus obliquus Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002798 spectrophotometry method Methods 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007180 physiological regulation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, 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
- C12N1/02—Separating microorganisms from their culture media
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/001—Agricultural products, food, biogas, algae
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/003—Biotechnological applications, e.g. separation or purification of enzymes, hormones, vitamins, viruses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Zoology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Microbiology (AREA)
- Biomedical Technology (AREA)
- Virology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Tropical Medicine & Parasitology (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses an application of a novel surfactant in microalgae froth flotation collection, wherein the novel surfactant shown in a formula I is used as a flotation collector in microalgae froth flotation collection. The novel surfactant is used as a flotation collector for microalgae froth flotation collection, the molecular structure of the novel surfactant contains two hydrophobic groups and a plurality of hydrophilic groups, the existence of double hydrophobic tail chains improves the hydrophobic capacity of the collector, and the existence of multiple hydrophilic head groups can promote the adsorption of collector molecules on the surfaces of microalgae and enhance the flotation performance of the collector molecules on the microalgae; compared with the collector used in the existing microalgae froth flotation collection technology, the collection efficiency and the recovery rate can be remarkably improved.
Description
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 recovery.
Background
At the moment of high-speed development in China, the problem of energy shortage caused by industrialization and town production is seriously faced. The microalgae biodiesel is prepared by converting microalgae into hydrocarbon substances through physiological regulation, or directly extracting grease from the microalgae by a high-temperature high-pressure liquefaction method, reacting to obtain fatty acid methyl ester with smaller relative molecular mass, and finally washing and drying (plant science journal, 2008, 26 (6): 650-660). The microalgae is a renewable biological energy source raw material, has the characteristics of short growth cycle, strong adaptability, good salt resistance, 60-70% of the dry weight of the cells and the like, and is suitable for large-scale industrialized culture (new energy development, 2018,6 (6): 467-474).
However, the existing researches mainly focus on the cultivation of microalgae, and few aspects related to algae harvesting are involved. According to data statistics, the energy consumption of the equipment for microalgae harvesting and enrichment accounts for 30% of the whole industrial production (Bioresource technology,2018, 269:188-194). Shen Ying and the like review the main technical means for microalgae harvesting and enrichment at present, namely sedimentation, filtration, centrifugation, flocculation and flotation (Hubei agricultural science, 2012, 51 (22): 4982-4991), but the former four methods have the problems of low energy consumption, long time consumption and the like, and severely restrict the development of the industry. 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 microalgae harvesting links at present.
Thea Coward et al utilized cetyl trimethylammonium bromide (see structural formula a) as a collector, demonstrating that flotation did have higher efficiency than the centrifugation methods currently used in commercial production (Biomass and Bioenergy,2014, (67): 354-362). The results of the comparison of a cationic collector Cetyl Trimethyl Ammonium Bromide (CTAB) and an anionic collector sodium dodecyl sulfate (SDS, shown in a structural formula b) by Chen Y.M. and the like show that the recovery rate of SDS to algae is about 10%, and the recovery rate of CTAB to algae can reach more than 90%; when SDS is used as a collector, 10mg/L 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 collector, and the influence of the consumption of the collector, the stirring rotation speed, the concentration of algae liquid, the pH of solution and the flotation time on the chlorella harvesting efficiency is researched by utilizing an orthogonal experiment, and the result shows that the optimal condition for harvesting the chlorella is that the consumption of 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 percent (renewable energy sources, 2016, 34 (2): 268-273). Patent CN201710712868.8, "a method for harvesting rhodococcus based on froth flotation", discloses a method for collecting floating products by froth flotation by combining rhamnolipid (see structural formula d) with a foaming agent. At present, the collector used in the froth flotation collection of microalgae is a traditional surfactant with a single hydrophobic group and a single hydrophilic group, and has the defects of poor selectivity, large dosage and weak collection capacity. Therefore, in order to solve the technical problem of poor flotation indexes in the current microalgae froth flotation collection, the novel efficient microalgae froth flotation collector with strong collection capacity and good selectivity is researched and developed, and has great significance on development and utilization of microalgae resources and sustainable development of agriculture and related industries. The present invention has been made in view of this.
(structural formula a: cetyl trimethylammonium bromide)
(structural formula b: sodium dodecyl sulfate)
CH 3 (CH 2 ) 10 CH 2 NH 2 (structural formula c: dodecylprimary amine)
(structural formula d: rhamnolipid)
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, providing a novel surfactant for collecting microalgae by froth flotation, which is used as a flotation collector, and solving the problems of poor selectivity, large consumption and weak collecting capacity in the process of collecting microalgae by the prior traditional surfactant with single hydrophobic group and single hydrophilic group, poor recovery rate and low enrichment ratio in the process of collecting microalgae by froth flotation, and high microalgae collecting cost.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
the novel surfactant is applied to microalgae froth flotation collection, and is used as a flotation collector in the microalgae froth flotation collection, wherein the novel surfactant is shown in a formula I, and the structure of the novel surfactant is shown in a formula I:
in the microalgae froth flotation collection, a novel surfactant shown in a formula I is used as a flotation collector, the pH value of the microalgae liquid for flotation is in a range of 7-10, and the algae cell density of the microalgae liquid is 1 multiplied by 10 8 cells/L～6×10 8 The dosage of the novel surfactant is 10-40 mg/L, and the microalgae is specifically one of chlorella, rhodococcus and scenedesmus.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects.
(1) The novel surfactant has a plurality of hydrophilic groups in the molecules of the flotation collector, has stronger action capability with the surfaces of microalgae, has better selectivity on the microalgae, can promote the adsorption of the collector molecules on the surfaces of the cells of the microalgae, and can improve the flotation enrichment ratio;
(2) The molecular of the micro algae collector has two hydrophobic groups, so that the hydrophobic capacity of the collector is increased, the collection capacity of the micro algae is stronger, and the flotation effect of the micro algae can be enhanced;
(3) The novel surfactant flotation collector has strong microalgae collecting capability and good selectivity, improves the enrichment ratio and recovery rate of microalgae collecting, solves the technical problems of large consumption of the collector and low enrichment ratio and recovery rate of microalgae in the traditional surfactant, and has good popularization and application values.
The following describes the embodiments of the present invention in further detail.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the following examples will be clearly and completely described, and the following examples are provided for illustrating the present invention but are not intended to limit the scope of the present invention.
The invention provides a novel surfactant for microalgae froth flotation harvesting, which has a structure shown in a formula I:
example 1
The algae cell density of the chlorella algae liquid to be harvested is 1.9344 multiplied by 10 8 The pH value of the algae liquid is 9, 35mL of the algae liquid is transferred to a flotation machine and stirred for 2min, the novel surfactant shown in the formula I is added into the flotation machine at a flotation concentration of 15mg/L, the mixture is stirred for 2min at a rotation speed of 2000rpm, the flotation is stopped after 3min, after the algae mud is removed, the tailing is weighed, and the cell density is measured by spectrophotometry. The recovery rate of the chlorella is 99.21% and the enrichment ratio is 25.
Example 2
The algae cell density of the chlorella algae liquid to be harvested is 5.1793 multiplied by 10 8 The pH value of the algae liquid is 7, 1500mL of the algae liquid is transferred to a flotation machine and stirred for 3min, a novel surfactant shown in a formula I or common collector cetyl trimethyl ammonium bromide is added to the flotation machine at a flotation concentration of 30mg/L, the mixture is stirred for 3min at a rotation speed of 2000rpm, the flotation is stopped after 10min, and after the algae mud is removed, the tailings are weighed and the cell density is measured by a spectrophotometry. When the novel surfactant shown in the formula I is adopted, the recovery rate of chlorella is 99.86% and the enrichment ratio is 21; and when the common collector cetyl trimethyl ammonium bromide is adopted, the recovery rate of the chlorella is 45.17 percent, and the enrichment ratio is 7. Compared with the common collector cetyl trimethyl ammonium bromide, the novel surfactant shown in the formula I has the advantages that the recovery rate of chlorella is increased by 54.69 percent, and the enrichment ratio is increased by 14 percent.
Example 3
Algae cells of chlorella algae liquid to be harvestedDensity is 3.0572 ×10 8 The pH value of the algae liquid is 10, 1000mL of the algae liquid is transferred to a flotation machine and stirred for 4min, the novel surfactant shown in the formula I is added into the flotation machine at a flotation concentration of 40mg/L, the mixture is stirred for 4min at a rotation speed of 2000rpm, the flotation is stopped after 8min, after the algae mud is removed, the tailing is weighed, and the cell density is measured by spectrophotometry. The recovery rate of the rhodococcus is calculated to be 95.53 percent, and the enrichment ratio is 18.
Example 4
The algae cell density of the chlorella algae liquid to be harvested is 1.0554 multiplied by 10 8 The pH value of the algae liquid is 8, 750mL of the algae liquid is transferred to a flotation machine and stirred for 3min, a novel surfactant shown in a formula I or a common collector, namely, dodecyl amine, is added into the flotation machine at a flotation concentration of 35mg/L, and is stirred for 3min at a rotation speed of 2000rpm, the flotation is stopped after 9min, after the algae mud is removed, the tailings are weighed, and the cell density is measured by a spectrophotometry. The recovery rate of the rhodococcus is 92.64% and the enrichment ratio is 23 when the novel surfactant shown in the formula I is adopted; and when the common collector is dodecyl amine, the recovery rate of the rhodococcus is 58.93 percent, and the enrichment ratio is 6. Compared with the common collector dodecanol, when the novel surfactant shown in the formula I is used, the recovery rate of the rhodococcus is improved by 33.71 percent, and the enrichment ratio is improved by 17 percent.
Example 5
The density of the algae cells of the scenedesmus obliquus liquid to be harvested is 4.4472 multiplied by 10 8 The pH value of the algae liquid is 8, 500mL of the algae liquid is transferred to a flotation machine and stirred for 3min, the novel surfactant shown in the formula I is added into the flotation machine at a flotation concentration of 20mg/L, the mixture is stirred for 3min at a rotation speed of 2000rpm, the flotation is stopped after 6min, after the algae mud is removed, the tailing is weighed, and the cell density is measured by spectrophotometry. The recovery rate of the scenedesmus obliquus is 97.53 percent and the enrichment ratio is 22.
Example 6
The density of the algae cells of the scenedesmus obliquus liquid to be harvested is 1.0317 multiplied by 10 8 Transferring 3000mL of algae solution into a flotation machine, stirring for 3min, and adding novel surfactant shown in formula I or common collector cetyl trimethyl ammonium bromide to obtain the final productThe flotation concentration of 16mg/L is added into a flotation machine, stirred at 2000rpm for 3min, the flotation is stopped after 9min, and after the algae mud is removed, the tailings are weighed and the cell density is determined by spectrophotometry. The calculation shows that when the novel surfactant shown in the formula I is adopted, the recovery rate of the scenedesmus obliquus is 98.42 percent, and the enrichment ratio is 26; and when the common collector cetyl trimethyl ammonium bromide is adopted, the recovery rate of the scenedesmus obliquus is 52.86 percent, and the enrichment ratio is 9. Compared with the common collector cetyl trimethyl ammonium bromide, the novel surfactant shown in the formula I has the advantages that the recovery rate of the scenedesmus obliquus is improved by 45.56 percent, and the enrichment ratio is improved by 17 percent.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (1)
1. The application of a surfactant in microalgae froth flotation recovery is characterized in that: in the microalgae froth flotation collection, a surfactant shown in a formula I is used as a flotation collector, the pH value of the microalgae liquid for flotation is in a range of 7-10, and the density of algae cells of the microalgae liquid is 1.0317 multiplied by 10 8 cells/L～5.1793×10 8 The dosage of the cell/L and the surfactant is 15-40 mg/L, and the microalgae is specifically one of chlorella, rhodococcus and scenedesmus;
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| WO1998028081A1 (en) * | 1996-12-20 | 1998-07-02 | Eastman Chemical Company | Method for dewatering microalgae with a bubble column |
| CN102127509A (en) * | 2010-01-19 | 2011-07-20 | 新奥科技发展有限公司 | Method, device and system for separating microalgae |
| CN102517146A (en) * | 2011-12-22 | 2012-06-27 | 江南大学 | Auxiliary method for extracting algal oil by surfactant in water phase |
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| US20110081706A1 (en) * | 2009-10-02 | 2011-04-07 | TransAlgae Ltd | Method and system for efficient harvesting of microalgae and cyanobacteria |
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| CN102517146A (en) * | 2011-12-22 | 2012-06-27 | 江南大学 | Auxiliary method for extracting algal oil by surfactant in water phase |
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| 基于泡沫浮选的能源微藻采收实验研究;张海阳等;《可再生能源》;CNKI;20160228;第34卷(第2期);第268-273页 * |
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