CN108559709B - Method for harvesting energy microalgae cells by using organosilane modified halloysite - Google Patents
Method for harvesting energy microalgae cells by using organosilane modified halloysite Download PDFInfo
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- CN108559709B CN108559709B CN201810450267.9A CN201810450267A CN108559709B CN 108559709 B CN108559709 B CN 108559709B CN 201810450267 A CN201810450267 A CN 201810450267A CN 108559709 B CN108559709 B CN 108559709B
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Abstract
The invention relates to a method for harvesting energy microalgae cells by using organosilane modified halloysite, which belongs to the field of biomass energy. The invention has the advantages of simple process flow, no influence on the reuse of the reclaimed water after harvesting and the extraction of the oil of the microalgae cells, high harvesting efficiency and the like, and is easy to realize popularization and application.
Description
Technical Field
The invention relates to a method for harvesting energy microalgae cells by using organosilane modified halloysite, belonging to the field of biomass energy.
Background
The microalgae have short growth cycle (about 20 g/m)2D), high oil content (more than or equal to 50% of dry cell weight), high yield (5000-2And nutrient elements in the wastewater are recycled, and the biomass energy is widely considered as the biomass energy which has the most potential to comprehensively replace fossil fuel in the future. However, energy microalgae as biomass energy has not been popularized and utilized, mainly due to its high production cost. In particular, in the harvesting step, the microalgae cells are small (2-40 μm), low in concentration (0.5-2g/L), negatively charged on the cell surface and hydrophilic, and can be stably suspended in a culture solution, so that the cost consumed by harvesting accounts for about 20-30% of the whole microalgae industrial chain.
Sedimentation is used as an economical and efficient solid-liquid separation method and is widely applied to the fields of mineral processing and water treatment. Because of the slow settling rate of nature, especially when dealing with fine and dense particles, a flocculation pretreatment is usually performed to increase the particle (floc) size and thus increase the settling rate. In addition, the clay minerals are utilized to remove the algae in the water body in the water treatment field, thereby achieving the purpose of controlling the algal bloom. However, natural minerals are less efficient and are used in larger quantities. Therefore, the clay mineral is modified by an inorganic or organic method to improve the removal efficiency. The modification is mainly to utilize inorganic metal salts (Al, Fe salts, etc.) and electropositive flocculating agents such as polymers thereof, etc. to adsorb to the surface of the adhered mineral (electronegative) through electrostatic action, namely a physical modification method. Then, after the modified clay mineral is dissolved in the water solution, the flocculating agent (or the intermediate) is dissolved out through the action of dissolution or hydrolysis and the like, so that the effect of flocculating the algae is achieved. The mechanism of action of this modified clay for removal/harvesting of algae is substantially similar to that of traditional flocculation: electrical neutralization or net capture. However, in the process of microalgae flocculation, flocculants are remained in water and microalgae organisms, thereby influencing the recycling of the recovered water and the extraction of grease after microalgae harvesting.
The invention comprises the following steps:
the invention aims to solve the problems that a flocculating agent pollutes backwater and biomass when microalgae cells are harvested by flocculation sedimentation at present, and provides a harvesting method for realizing quick co-sedimentation of the microalgae cells and halloysite by utilizing electropositive organosilane modified halloysite to adsorb the microalgae cells with negative electricity.
The specific technical scheme is as follows:
the method for harvesting energy microalgae cells by using organosilane modified halloysite comprises the following steps:
adding the organosilane modified halloysite into an energy microalgae solution, wherein the adding amount is 0.25-3.0 g/g based on the mass of the modified halloysite/dry weight of microalgae cells;
and adjusting the pH value of the mixed solution to 2-11 by using 1mol/L HCl or NaOH solution, rapidly stirring for 30s at 200rpm and slowly stirring for 3min at 50rpm by using a stirrer, and standing for 15 min.
Wherein, the halloysite is modified by organosilane, and the surface of the halloysite is positively charged by the organosilane modification in a chemical grafting way. The preparation method of the organosilane modified halloysite comprises the following raw materials in parts by weight:
dissolving 1-10 mL of 3-aminopropyltrimethoxysilane in 50-200 mL of ethanol solution, adding 2-10 g of halloysite, heating and carrying out reflux reaction for 6-24 h under the stirring of the rotation speed of 400 rpm;
and (3) centrifugally separating, washing a solid product for 3 times by using an ethanol solvent, and finally drying the obtained solid in a drying oven at 105 ℃ to obtain the organosilane modified halloysite.
The modified mineral applied in the process is characterized in that organosilane is grafted on halloysite through chemical action, so that the modified halloysite is positively charged; then, under the electrostatic action, the microalgae cells are adsorbed on the surface of the modified halloysite; due to the halloysite density (2.55-2.65 g/cm)3Average density 2.59g/cm3) Algae cells/flocs (1.0-1.1 g/cm)3) Therefore, the sedimentation rate of the co-sedimentation is higher than that of the traditional flocculation sedimentation, which is hopeful to realize the high-efficiency and pollution-free harvest of microalgae cells and accelerate the industrialization process of energy microalgae.
The main principle of the invention is as follows: organosilane and hydroxyl on the surface of the halloysite are subjected to covalent grafting, functional groups (such as amino, aminopropyl and the like) are introduced to the surface of the halloysite, and the charge property of the surface of the halloysite is changed, so that the modified halloysite is positively charged under a certain pH condition. Since most microalgae have a negative cell surface in the pH range of 2-11. Thus, the microalgae cells and the modified halloysite surfaces can be charged oppositely by adjusting the pH of the microalgae solution during harvesting. Under the action of electrostatic attraction, the microalgae cells are adsorbed on the surface of the modified halloysite to form microalgae cell-mineral particle aggregates (non-microalgae flocs). Because the halloysite mineral density is higher, the density of the microalgae cell-mineral particle aggregate formed in the method is higher than that of a microalgae floc formed by traditional flocculation, and therefore, the efficient harvesting of the microalgae cells is realized.
The advantages and positive effects of the invention are reflected in the following points:
1. according to the invention, organosilane is fully utilized to carry out chemical modification on the halloysite, so that the surface of the halloysite is positively charged; meanwhile, the modified halloysite can not dissolve out chemical agents again in an aqueous solution, so that the influence on the recycling of the harvested backwater and microalgae biomass is avoided.
2. According to the invention, the characteristic of positive charge of the modified halloysite is utilized, and microalgae cells with negative charge are adsorbed through electrostatic action to form a microalgae cell-modified halloysite aggregate. Because the halloysite is higher in density than microalgae cells, the co-sedimentation speed of the modified halloysite is higher than that of the traditional flocculation sedimentation.
The invention has the advantages of simple process flow, no influence on the reuse of the reclaimed water after harvesting and the extraction of the oil of the microalgae cells, high harvesting efficiency and the like, and is easy to realize popularization and application.
Drawings
FIG. 1 is a graph of zeta potential of halloysite before and after modification with organosilane in the examples.
FIG. 2 is a graph comparing the efficiency of harvesting microalgae cells from organosilane modified halloysite in the examples.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
The specific technical scheme for realizing the aim of the invention sequentially comprises the following steps:
example 1
1) Preparation of organosilane-modified halloysite: dissolving 10mL of 3-aminopropyltrimethoxysilane in 200mL of ethanol solution, adding 10g of halloysite sample, heating and refluxing for 24h under the stirring of 400rpm, centrifugally separating, washing a solid product with a fresh ethanol solvent for 3 times, and finally placing the obtained solid in an oven at 105 ℃ for drying to obtain the organosilane modified halloysite sample.
The zeta potential patterns of the halloysite before and after modification by the obtained product of organosilane are shown in figure 1.
2) Harvesting energy microalgae cells from the modified halloysite: adding the organosilane modified halloysite obtained in the step 1) into an energy microalgae solution, wherein the adding amount is 1g/g (based on the mass of the modified halloysite/dry weight of microalgae cells). Adjusting the pH value of the mixed solution to 3 by using 1mol/L HCl or NaOH solution, rapidly stirring for 30s at 200rpm by using a stirrer, slowly stirring for 3min at 50rpm, standing for 15min, and measuring the light absorption values of the microalgae solution before and after harvesting (supernatant) by using an ultraviolet spectrophotometer to calculate the harvesting efficiency to 95.70%.
This example is shown in fig. 2 for a plot of settling rate versus natural settling, conventional flocculation settling, and unmodified halloysite harvested energy microalgae cells.
Example 2
1) Preparation of organosilane-modified halloysite: dissolving 5mL of 3-aminopropyltrimethoxysilane in 100mL of ethanol solution, adding 10g of halloysite sample, heating and refluxing for 12h under the stirring of 400rpm, centrifugally separating, washing a solid product with a fresh ethanol solvent for 3 times, and finally placing the obtained solid in an oven at 105 ℃ for drying to obtain the organosilane modified halloysite sample.
2) Harvesting energy microalgae cells from the modified halloysite: adding the organosilane modified halloysite obtained in the step 1) into an energy microalgae solution, wherein the adding amount is 3g/g (based on the mass of the modified halloysite/dry weight of microalgae cells). Adjusting the pH value of the mixed solution to 3 by using 1mol/L HCl or NaOH solution, rapidly stirring for 30s at 200rpm by using a stirrer, slowly stirring for 3min at 50rpm, standing for 15min, and measuring the light absorption values of the microalgae solution before and after harvesting (supernatant) by using an ultraviolet spectrophotometer to calculate the harvesting efficiency to 98.21%.
Example 3
1) Preparation of organosilane-modified halloysite: dissolving 10mL of 3-aminopropyltrimethoxysilane in 100mL of ethanol solution, adding 10g of halloysite sample, heating and refluxing for 10h under the stirring of 400rpm, centrifugally separating, washing a solid product with a fresh ethanol solvent for 3 times, and finally placing the obtained solid in an oven at 105 ℃ for drying to obtain the organosilane modified halloysite sample.
2) Harvesting energy microalgae cells from the modified halloysite: adding the organosilane modified halloysite obtained in the step 1) into an energy microalgae solution, wherein the adding amount is 0.25g/g (based on the mass of the modified halloysite/dry weight of microalgae cells). Adjusting the pH value of the mixed solution to 3 by using 1mol/L HCl or NaOH solution, rapidly stirring for 30s at 200rpm by using a stirrer, slowly stirring for 3min at 50rpm, standing for 15min, and measuring the light absorption values of the microalgae solution before and after harvesting (supernatant) by using an ultraviolet spectrophotometer to calculate the harvesting efficiency to 74.65%.
Example 4
1) Preparation of organosilane-modified halloysite: dissolving 3-aminopropyltrimethoxysilane in 5mL in 100mL of ethanol solution, adding a halloysite sample in 5g, heating and refluxing for reaction for 12h under the stirring of 400rpm, centrifugally separating, washing a solid product with a fresh ethanol solvent for 3 times, and finally drying the obtained solid in an oven at 105 ℃ to obtain the organosilane modified halloysite sample.
2) Harvesting energy microalgae cells from the modified halloysite: adding the organosilane modified halloysite obtained in the step 1) into an energy microalgae solution, wherein the adding amount is 1g/g (based on the mass of the modified halloysite/dry weight of microalgae cells). Adjusting the pH value of the mixed solution to 11 by using 1mol/L HCl or NaOH solution, rapidly stirring for 30s at 200rpm by using a stirrer, slowly stirring for 3min at 50rpm, standing for 15min, and measuring the light absorption values of the microalgae solution before and after harvesting (supernatant) by using an ultraviolet spectrophotometer to calculate the harvesting efficiency to be 14.48%.
Claims (1)
1. The method for harvesting energy microalgae cells by using organosilane modified halloysite is characterized by comprising the following steps of:
dissolving 1-10 mL of 3-aminopropyltrimethoxysilane in 50-200 mL of ethanol solution, adding 2-10 g of halloysite, heating and carrying out reflux reaction for 6-24 h under the stirring of the rotation speed of 400 rpm; centrifuging, washing the solid product with ethanol solvent for 3 times, and drying the obtained solid in a drying oven at 105 ℃ to obtain organosilane modified halloysite;
adding organosilane modified halloysite into an energy microalgae solution, wherein the adding amount is 0.25-3.0 g/g of the mass of the modified halloysite/dry weight of microalgae cells;
the pH = 3 of the mixture was adjusted with 1mol/L HCl or NaOH solution, and the mixture was rapidly stirred at 200rpm for 30s and slowly stirred at 50rpm for 3min, and then allowed to stand for 15 min.
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Citations (4)
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