CN106845128B - Microalgae flotation efficiency prediction device and method based on microalgae surface characteristics - Google Patents
Microalgae flotation efficiency prediction device and method based on microalgae surface characteristics Download PDFInfo
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- 238000005188 flotation Methods 0.000 title claims abstract description 173
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 143
- 238000001514 detection method Methods 0.000 claims abstract description 75
- 238000012545 processing Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 25
- 239000000523 sample Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000005411 Van der Waals force Methods 0.000 claims description 17
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- 238000004891 communication Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 7
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- 241000195633 Dunaliella salina Species 0.000 claims description 3
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Abstract
The invention discloses a microalgae flotation efficiency prediction device and method based on microalgae surface characteristics, wherein the prediction device comprises a controller, a contact angle detection module, a Zeta potential measuring instrument and data processing equipment, wherein the input end of the controller is connected with an air flow meter, a PH detection meter, a parameter setting module and a timer, and the output end of the controller is connected with a stirring module, a centrifugal module and a display; the prediction method comprises the following steps: step one, measuring contact angles of microalgae and detection liquid; step two, measuring the Zeta potential of the microalgae; thirdly, calculating the free energy of the surface of the microalgae; step four, microalgae flotation; fifthly, calculating microalgae flotation efficiency; and step six, obtaining the relation between the floatation efficiency and the free energy of the microalgae surface. The invention can obtain the relation between the flotation efficiency and the free energy of the microalgae surface, accurately and reliably predict the flotation efficiency of the microalgae under different free energies of the surfaces, and provide a basis for the high-efficiency flotation condition of the microalgae.
Description
Technical Field
The invention belongs to the technical field of microalgae flotation, and particularly relates to a microalgae flotation efficiency prediction device and method based on microalgae surface characteristics.
Background
At present, the economy is rapidly developed, the energy demand is continuously increased, the fossil fuel can not meet the normal demand of human beings, and the development of sustainable production fossil to replace fuel becomes the dominant direction of energy development in the future. The biodiesel is prepared from energy microalgae, and is widely and continuously focused in the past ten years as an emerging biomass industry, so that the biodiesel becomes a research hotspot in the field of biological energy. Algae is an important renewable resource, and has the outstanding characteristics of wide distribution, large biomass, high photosynthetic efficiency, strong environment adaptability, short growth period, high grease content, environmental friendliness and the like. Algae, particularly microalgae, will become an important biomass for providing new energy and resources. According to research, the cost consumed by the flotation link in the microalgae industrial chain accounts for 20% -30% of the whole production cost, and large-scale low-energy-consumption efficient economic continuous flotation is an important link of industrial application of microalgae, so that the research and development of novel separation methods and technologies reduce the flotation cost and energy consumption, and improve the microalgae product quality to meet the requirements of microalgae industrial development.
The solution air floatation method for recovering the activated sludge in the wastewater treatment process is reported at the earliest, and is gradually applied to the microalgae floatation process after continuous development. The dissolved air flotation method is to dissolve air in water under a certain pressure, and then separate out the dissolved air under a reduced pressure condition to form micro bubbles. The pressure of the gas bubbles can be divided into two types, namely a vacuum gas-floating method and a pressurized gas-containing gas-floating method according to the difference of the pressure of the gas bubbles during precipitation. When the method is applied to microalgae flotation, the basic flow is that air is introduced under a certain pressure, the microalgae flotation is in a saturated dissolution state in water, air bubbles adhere to the microalgae clusters to reduce the overall density of the flocculation clusters, then the pressure is suddenly reduced, the gas solubility is reduced, the dissolved air in the water is separated out of the water body to form micro air bubbles with the diameter of 0.01-0.1 mm, the air bubbles with high concentration and uniform granularity float upwards, and the loose microalgae flocculation clusters are driven to float on the water surface for collection. The adhesion capacity of microalgae to bubbles is a key to determine the microalgae flotation efficiency, and is determined by the surface characteristics of microalgae, namely the free energy of the microalgae surface. For hydrophilic microalgae, because bubbles and water are easier to adhere to each other, the direct flotation effect is poor, and a proper flotation agent is required to be added to change the surface free energy of the microalgae so that the microalgae are easier to adhere to the bubbles, so that higher flotation efficiency can be obtained; for microalgae with low hydrophobicity, proper flotation agents are also required to be added to enhance the surface free energy of the microalgae. In addition, the free energy of the microalgae surface can also be influenced by the pH value of the growing environment. However, at present, no related research is made on the relation between the free energy of the microalgae surface and the flotation efficiency of the flotation agent, and the relation between the flotation efficiency and the free energy of the microalgae surface can not be obtained, so that the flotation efficiency of the microalgae under different free energies of the surfaces can not be accurately and reliably predicted, and a basis is provided for the microalgae flotation conditions. Therefore, a microalgae flotation efficiency prediction device and a microalgae flotation efficiency prediction method based on microalgae surface characteristics, which are simple and convenient to operate, convenient to implement and good in use effect, can acquire the relation between the flotation efficiency and the free energy of the microalgae surface, accurately and reliably predict the flotation efficiency of the microalgae under different free energies of the surfaces, and provide a basis for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the microalgae flotation efficiency prediction device based on the microalgae surface characteristics, which has reasonable design, simple and convenient operation and good use effect, can acquire the relation between the flotation efficiency and the free energy of the microalgae surface, accurately and reliably predicts the flotation efficiency of the microalgae under different free energies of the surfaces, and provides a basis for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
In order to solve the technical problems, the invention adopts the following technical scheme: microalgae flotation efficiency prediction device based on microalgae surface characteristics is characterized in that: the device comprises a controller, a contact angle detection module, a Zeta potential measuring instrument for detecting microalgae Zeta potential, and data processing equipment connected with the controller, wherein the input end of the controller is connected with an air flow meter, a PH detection meter and a timer, the output end of the controller is connected with a stirring module, a centrifugal module and a display, the contact angle detection module comprises a camera and an image acquisition module connected with the output end of the camera, and the image acquisition module is connected with the controller.
The microalgae flotation efficiency prediction device based on the microalgae surface characteristics is characterized in that: the system also comprises a memory and a parameter setting module, wherein the memory and the parameter setting module are connected with the controller.
The microalgae flotation efficiency prediction device based on the microalgae surface characteristics is characterized in that: the data processing device is a computer, and the computer is in bidirectional communication with the controller through the data communication module.
The microalgae flotation efficiency prediction device based on the microalgae surface characteristics is characterized in that: the Zeta potential measuring instrument comprises a laser generating device for generating laser and a detection needle for detecting the Zeta potential of the microalgae.
The microalgae flotation efficiency prediction device based on the microalgae surface characteristics is characterized in that: the data communication module is an RS232 serial communication interface circuit or an RS485 serial communication interface circuit.
Meanwhile, the invention also discloses a microalgae flotation efficiency prediction method which has the advantages of simple steps, reasonable design, convenient realization and good use effect, and is characterized in that: the method comprises the following steps:
step one, measuring contact angles of microalgae and detection liquid, wherein the measurement process comprises the following steps:
step 101, washing microalgae liquid and regulating pH: washing the microalgae liquid twice by deionized water, adding an HCL solution or a NaOH solution into the washed microalgae liquid, detecting the pH value of the washed microalgae liquid in real time by a pH detector, and sending the detected pH value of the washed microalgae liquid to a controller to enable the pH value of the washed microalgae liquid to be 5-10, so as to obtain the microalgae liquid to be treated;
step 102, centrifuging microalgae liquid to be treated: placing the microalgae liquid to be treated obtained in the step 101 into a centrifugal cup containing deionized water, and then placing the centrifugal cup into a centrifugal module for centrifugal treatment to obtain the microalgae liquid to be treated after centrifugal treatment;
step 103: manufacturing of algae lawn: extracting 1-2 mL of the lower microalgae solution of the microalgae solution to be treated after the centrifugation in the step 102 by using a syringe to obtain filtrate; spreading 4-5 drops of the filtrate on a glass slide, and naturally airing the glass slide at normal temperature to prepare an algae lawn;
step 104: detection of microalgae and probe liquid contact angle: the method comprises the steps that the injector is adopted to enable detection liquid to be dropped on an algae level manufactured in step 103, a microalgae detection liquid measurement sample is obtained, when the time set by a timer is reached, a camera is used for collecting images of the microalgae detection liquid measurement sample, the collected images of the microalgae detection liquid measurement sample are sent to data processing equipment through an image collecting module and a controller, the data processing equipment calls a contact angle calculating module to obtain a microalgae contact angle theta and a detection liquid contact angle theta, the detected microalgae contact angle theta and the detected detection liquid contact angle theta are sent to the controller, and the microalgae contact angle theta and the detection liquid contact angle theta are synchronously displayed through a display;
step two, measuring the Zeta potential of the microalgae, wherein the process is as follows:
step 201, manufacturing a microalgae measurement sample: firstly adding HCL solution or NaOH solution into microalgae solution, detecting the PH value of the microalgae solution in real time by a PH detector, sending the detected PH value of the microalgae solution to a controller to enable the PH value of the microalgae solution to be 5-10, obtaining microalgae solution to be detected, taking 10mL of microalgae solution to be detected from the microalgae solution to be detected, placing the microalgae solution to be detected into a test tube, standing the test tube for 10-15 min, and then taking supernatant from the test tube to obtain a microalgae determination sample;
step 202, measuring the Zeta potential of the microalgae: detecting the microalgae measurement sample obtained in the step 201 by adopting a Zeta potential measuring instrument, sending the detected microalgae Zeta potential to a controller, synchronously displaying the microalgae Zeta potential through a display, and selecting a floatation agent cetyl trimethyl ammonium bromide according to the microalgae Zeta potential;
step three, calculating the free energy of the microalgae surface: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy of the detection liquid, wherein +.>
For detecting Van der Waals forces of the fluid, +.>
To detect the electron-withdrawing ability of the liquid, +.>
The electron losing capacity of the detection liquid; then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the free energy delta G of the surface of the microalgae coh ；
Step four, microalgae flotation: firstly, 1.0L of microalgae liquid is put into a conical flask, the conical flask is put into a stirring module and is stirred for 2-4 min, then 1.0L of microalgae liquid in the conical flask is put into a flotation tank, then HCL solution or NaOH solution is added into the flotation tank, the PH value of the microalgae liquid in the flotation tank is detected in real time through a PH detector, the detected PH value of the microalgae liquid in the flotation tank is sent to a controller, the PH value of the microalgae liquid in the flotation tank is 5-10, 45-55 mg/L of cetyltrimethylammonium bromide is added into the flotation tank, the flotation tank is inflated after the rotating speed of the flotation tank is regulated to 800-1000 rpm and is stirred for 5-7 min, the inflated flow is detected in real time through an air flowmeter and is sent to the controller, the detected inflated flow is enabled to be 180-200L/h, flotation is carried out while stirring, and a tailing is obtained, wherein the time is 10-15 min;
step five, calculating microalgae flotation efficiency: with the data processing apparatus and according to the formula
Obtaining flotation efficiency W, wherein T represents the weight of the tailings, F represents the weight of 1.0L of microalgae liquid, alpha represents the density of microalgae in 1.0L of microalgae liquid, and beta represents the density of microalgae in the tailings;
step six, obtaining the relation between the flotation efficiency and the free energy of the microalgae surface: in the first step, the PH value of the microalgae solution is p 1 、p 2 、p 3 、...、p n When the free energy of the microalgae surface is respectively obtained as delta G coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn Meanwhile, in the fifth step, the pH value of the microalgae solution in the flotation tank is p 1 、p 2 、p 3 、...、p n Respectively obtain flotation efficiency W 1 、W 2 、W 3 、...、W n The method comprises the steps of carrying out a first treatment on the surface of the Drawing software is called by adopting the data processing equipment to obtain free energy delta G of the microalgae surface cohi On the abscissa, flotation efficiency W i On the ordinate, the free energy DeltaG of the microalgae surface is drawn coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn And flotation efficiency W 1 、W 2 、W 3 、...、W n Corresponding each point, and fitting to obtain the free energy delta G of the microalgae surface cohi And flotation efficiency W i The relation curves and expressions are synchronously displayed through a display, wherein the values of i are 1, 2, 3, n and 5 is less than or equal to p respectively 1 ＜p 2 ＜p 3 ＜....＜p n ≤10。
The microalgae flotation efficiency prediction method is characterized by comprising the following steps of: the rotational speed of the centrifugal treatment in the step 101 is 2500 rpm-3000 rpm, and the time of the centrifugal treatment is 5 min-10 min.
The microalgae flotation efficiency prediction method is characterized by comprising the following steps of: the detection liquid comprises deionized water, ethylene glycol and diiodomethane, and the value of l is 1, 2 and 3 respectively;
when the detection liquid is ionized water, glycol and diiodomethane in the step 104, respectively obtaining a contact angle theta 1 of microalgae and ionized water, a contact angle theta 2 of microalgae and glycol and a contact angle theta 3 of microalgae and diiodomethane;
in the third step, the free energy of the microalgae surface is calculated, and the specific process is as follows: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy gamma of deionized water 1 Total surface energy gamma of ethylene glycol 2 And diiodomethane surface energy gamma 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>
Van der Waals force of deionized water, +.>
For deionized water to gain electronic ability,/o>
For de-ionized water electron-withdrawing ability->
Van der Waals force of ethylene glycol, +.>
For the electron gain of ethylene glycol, +.>
Is the electron-losing ability of glycol, +.>
Van der Waals force for diiodomethane, < >>
For diiodomethane electron-obtaining ability, +.>
Electron-losing ability of diiodomethane;
then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the free energy delta G of the surface of the microalgae coh 。
The microalgae flotation efficiency prediction method is characterized by comprising the following steps of: the microalgae liquid is chlorella liquid, anabaena liquid, rhodococcus liquid, phaeodactylum tricornutum liquid or Dunaliella salina liquid.
The microalgae flotation efficiency prediction method is characterized by comprising the following steps of: the time set by the timer in step 104 is 0.5s;
the diameter of the syringe needle is 0.2mm.
Compared with the prior art, the invention has the following advantages:
1. the microalgae flotation efficiency prediction device is simple in structure, reasonable in design, low in input cost and convenient to install and arrange.
2. The adopted microalgae flotation efficiency prediction device has comprehensive functions, the contact angle of microalgae and detection liquid is detected by arranging a contact angle detection module, free energy of the surfaces of the microalgae is obtained through data processing equipment, the Zeta potential of the microalgae is detected by arranging a Zeta potential measuring instrument, a flotation agent is selected according to the Zeta potential of the microalgae, the PH value of the washed microalgae liquid and the PH value of the microalgae liquid in the flotation tank can be detected in real time by arranging a PH detector, the PH value of the washed microalgae liquid and the PH value of the microalgae liquid in the flotation tank meet the requirements, and the accuracy of data is ensured; the centrifugal treatment of the microalgae liquid to be treated is realized by arranging a centrifugal module, so that the prepared algae plateau is convenient for detecting the contact angle of the microalgae and the detection liquid; the stirring module is arranged to stir microalgae liquid in the conical flask, so that microalgae precipitation is avoided, and the aeration flow of the flotation tank is detected in real time by arranging the air flowmeter, so that the aeration flow of the flotation tank is ensured to meet the requirement, and the flotation effect of the microalgae is ensured; the timer is arranged to ensure that the camera collects microalgae detection liquid measurement sample images with set time, so that shaking of the detection liquid just dropping on the algae level is avoided, the influence of gravity of the detection liquid is avoided, and the detection accuracy of the contact angle of the microalgae and the detection liquid is improved.
3. The adopted microalgae flotation efficiency prediction device is simple and convenient to operate, the image of a microalgae detection liquid measurement sample is acquired in real time through a camera, the image is sent to data processing equipment for processing through an image acquisition module and a controller, the contact angle of the microalgae and the detection liquid is obtained, and the free energy of the surface of the microalgae is obtained according to the contact angle of the microalgae and the detection liquid; the flotation efficiency is obtained through microalgae flotation, so that the relation between the flotation efficiency and the free energy of the microalgae surface is obtained, the flotation efficiency of the microalgae under different free energies of the surfaces is accurately and reliably predicted, and a basis is provided for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
4. The adopted microalgae flotation efficiency prediction device can detect the pH value of the microalgae liquid after washing, the pH value of the microalgae liquid in the flotation tank and the aeration flow in real time, and can control the stirring time of the stirring module, the rotating speed of centrifugal treatment and the time of centrifugal treatment in real time, so that the intelligent control of the microalgae flotation efficiency prediction device is realized, and the operation requirement is met to the greatest extent.
5. The microalgae flotation efficiency prediction method is simple in steps and accurate in calculation, and the microalgae flotation efficiency prediction calculation process is integrated by adopting data processing equipment, so that complicated manual calculation can be reduced, and the accuracy of a calculation result is improved through a high-precision function.
6. The adopted microalgae flotation efficiency prediction method is reasonable in design, firstly, the contact angle of microalgae and detection liquid is detected by a contact angle detection module, and free energy of the microalgae surface is obtained by data processing equipment; detecting the Zeta potential of the microalgae by a Zeta potential measuring instrument, and selecting a flotation agent according to the Zeta potential of the microalgae; then adding the microalgae liquid and a flotation agent into a flotation tank for flotation, and calculating to obtain microalgae flotation efficiency; and finally, acquiring free energy of the microalgae surface under different pH values of the microalgae liquid, and acquiring flotation efficiency under different pH values of the microalgae liquid in the flotation tank to obtain the relationship between the free energy of the microalgae surface and the flotation efficiency.
7. The microalgae flotation efficiency prediction method is convenient to realize and good in use effect, can acquire the relation between the flotation efficiency and the free energy of the microalgae surface, and accurately and reliably predicts the flotation efficiency of the microalgae under different free energies of the surfaces. In the actual use process, the flotation efficiency of the flotation agent is predicted, so that the flotation effect of the flotation agent on microalgae can be simply, rapidly and accurately judged, and a basis is provided for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
In conclusion, the method has the advantages of reasonable design, simple and convenient operation and good use effect, obtains the relation between the flotation efficiency and the free energy of the microalgae surface, accurately and reliably predicts the flotation efficiency of the microalgae under different free energies of the surfaces, and provides a basis for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
Fig. 1 is a schematic block diagram of a microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics.
FIG. 2 is a block flow diagram of the prediction method of the present invention.
FIG. 3 is a graph showing the relationship between the free energy of chlorella surface and the flotation efficiency in example 2 of the present invention.
FIG. 4 is a graph showing the relationship between the free energy of the surface of anabaena and the flotation efficiency in example 3 of the present invention.
FIG. 5 is a graph showing the relationship between the free energy of the surface of Synechococcus and the flotation efficiency in example 4 of the present invention.
Reference numerals illustrate:
1-a controller; 2-an air flow meter; 3-a video camera;
4, an image acquisition module; 5-Zeta potential measuring instrument; 6, a timer;
7, a stirring module; 8-a display; 9-a memory;
10-a parameter setting module; 11-a centrifugal module; 12-a data communication module;
13-a computer; 14-PH meter.
Detailed Description
As shown in fig. 1, the microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics of the present invention is described in detail by way of example 1.
Example 1
The embodiment comprises a controller 1, a contact angle detection module, a Zeta potential measuring instrument 5 for detecting microalgae Zeta potential, and data processing equipment connected with the controller 1, wherein the input end of the controller 1 is connected with an air flow meter 2, a PH detector 14 and a timer 6, the output end of the controller 1 is connected with a stirring module 7, a centrifugal module 11 and a display 8, the contact angle detection module comprises a camera 3 and an image acquisition module 4 connected with the output end of the camera 3, and the image acquisition module 4 is connected with the controller 1.
In this embodiment, the device further comprises a memory 9 and a parameter setting module 10, and the memory 9 and the parameter setting module 10 are connected with the controller 1.
In this embodiment, the aeration flow, the stirring time, the centrifugation time and the centrifugation rotation speed of the flotation tank can be preset by setting the parameter setting module 10, so that the operation control is facilitated.
In this embodiment, the method is characterized in that: the data processing device is a computer 13, and the computer 13 is in bidirectional communication with the controller 1 through the data communication module 12.
In this embodiment, the Zeta potential meter 5 includes a laser generating device for generating laser light and a probe for detecting the Zeta potential of microalgae.
In this embodiment, the data communication module 12 is an RS232 serial communication interface circuit or an RS485 serial communication interface circuit.
As shown in fig. 2, the microalgae flotation efficiency prediction method based on the microalgae surface characteristics of the present invention is described by examples 2 to 4:
example 2
The embodiment comprises the following steps:
step one, measuring contact angles of microalgae and detection liquid, wherein the measurement process comprises the following steps:
step 101, washing microalgae liquid and regulating pH: washing the microalgae liquid twice by deionized water, adding an HCL solution or a NaOH solution into the washed microalgae liquid, detecting the PH value of the washed microalgae liquid in real time by a PH detector 14, and sending the detected PH value of the washed microalgae liquid to a controller 1 to enable the PH value of the washed microalgae liquid to be 5-10, thus obtaining the microalgae liquid to be treated;
in this embodiment, the rotational speed of the centrifugal treatment in step 101 is 2500rpm, and in the actual use process, the rotational speed of the centrifugal treatment can be adjusted within the range of 2500rpm to 3000rpm according to specific requirements. The time of the centrifugal treatment is 5min, and the time of the centrifugal treatment can be adjusted within the range of 5 min-10 min according to specific requirements in the actual use process.
Step 102, centrifuging microalgae liquid to be treated: placing the microalgae liquid to be treated obtained in the step 101 into a centrifugal cup containing deionized water, and then placing the centrifugal cup into a centrifugal module 11 for centrifugal treatment to obtain the microalgae liquid to be treated after centrifugal treatment;
in this embodiment, the microalgae liquid to be treated is subjected to centrifugal treatment by the centrifugal module 11, so that the algae plateau can be made to facilitate detection of the contact angle of microalgae and detection liquid.
Step 103: manufacturing of algae lawn: extracting 1mL of the lower microalgae solution of the microalgae solution to be treated after the centrifugation in the step 102 by using a syringe to obtain filtrate; spreading 4-5 drops of the filtrate on a glass slide, and naturally airing the glass slide at normal temperature to prepare an algae lawn;
step 104: detection of microalgae and probe liquid contact angle: the method comprises the steps that the injector is adopted to enable detection liquid to be dropped on an algae level manufactured in step 103, a microalgae detection liquid measurement sample is obtained, when the time set by a timer 6 is reached, a camera 3 collects images of the microalgae detection liquid measurement sample, the collected images of the microalgae detection liquid measurement sample are sent to data processing equipment through an image collection module 4 and a controller 1, the data processing equipment calls a contact angle calculation module to obtain microalgae and detection liquid contact angle theta, the detected microalgae and detection liquid contact angle theta is sent to the controller 1, and the microalgae and detection liquid contact angle theta is synchronously displayed through a display 8;
in this embodiment, the syringe needle has a diameter of 0.2mm.
In this embodiment, the detection solution includes deionized water, ethylene glycol, and diiodomethane.
In this embodiment, when the detection liquid is ionized water, ethylene glycol and diiodomethane in step 104, the contact angle θ1 of microalgae and ionized water, the contact angle θ2 of microalgae and ethylene glycol and the contact angle θ3 of microalgae and diiodomethane are obtained respectively.
In this embodiment, the timer 6 is used to set the time, so as to ensure that the camera 3 collects the microalgae detection liquid measurement sample image with the set time, avoid shaking of the detection liquid just dropping on the algae level, avoid the influence of gravity of the detection liquid, and improve the detection accuracy of the contact angle of the microalgae and the detection liquid.
In this embodiment, the time set by the timer 6 in step 104 is 0.5s.
Step two, measuring the Zeta potential of the microalgae, wherein the process is as follows:
step 201, manufacturing a microalgae measurement sample: firstly adding HCL solution or NaOH solution into microalgae solution, detecting the PH value of the microalgae solution in real time by a PH detector 14, sending the detected PH value of the washed microalgae solution to a controller 1 to enable the PH value of the microalgae solution to be 5-10, obtaining microalgae solution to be detected, taking 10mL of microalgae solution to be detected from the microalgae solution to be detected, placing the microalgae solution into a test tube, standing the test tube for 10min, and then taking supernatant from the test tube to obtain a microalgae determination sample;
in this embodiment, the test tube in step 201 is kept stand for 10min, and in the actual use process, the time for keeping the test tube stand can be adjusted within the range of 10 min-15 min according to specific requirements.
Step 202, measuring the Zeta potential of the microalgae: detecting the microalgae measurement sample obtained in the step 201 by adopting a Zeta potential measuring instrument 5, sending the detected microalgae Zeta potential to a controller 1, synchronously displaying the microalgae Zeta potential through a display 8, and selecting a floatation agent cetyl trimethyl ammonium bromide according to the microalgae Zeta potential;
in the actual operation process, the microalgae Zeta potential is detected, the flotation agent is selected, and the potential of the flotation agent is opposite to the microalgae Zeta potential.
Step three, calculating the free energy of the microalgae surface: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy of the detection liquid, wherein +.>
For detecting Van der Waals forces of the fluid, +.>
To detect the electron-withdrawing ability of the liquid, gamma l - The electron losing capacity of the detection liquid; then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the free energy delta G of the surface of the microalgae coh ；
In this embodiment, the detection solution includes deionized water, ethylene glycol and diiodomethane, and the values of l are 1, 2 and 3 respectively;
when the detection liquid is ionized water, glycol and diiodomethane in the step 104, respectively obtaining a contact angle theta 1 of microalgae and ionized water, a contact angle theta 2 of microalgae and glycol and a contact angle theta 3 of microalgae and diiodomethane;
in the third step, the free energy of the microalgae surface is calculated, and the specific process is as follows: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy gamma of deionized water 1 Total surface energy gamma of ethylene glycol 2 And diiodomethane surface energy gamma 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>
Is deionized waterVan der Waals force, < >>
For deionized water to gain electronic ability,/o>
For de-ionized water electron-withdrawing ability->
Van der Waals force of ethylene glycol, +.>
For the electron gain of ethylene glycol, +.>
Is the electron-losing ability of glycol, +.>
Van der Waals force for diiodomethane, < >>
For diiodomethane electron-obtaining ability, +.>
Is diiodomethane electron-withdrawing ability as shown in table 1;
TABLE 1 parameters of the detection liquids (MJ/m 2 )
| Name of the name | γ l LW | γ l + | γ l - |
| Deionized water | 21.8 | 25.5 | 25.5 |
| Ethylene glycol | 29.0 | 1.92 | 47.0 |
| Diiodomethane | 50.8 | 0 | 0 |
Then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the micro-scaleAlgae surface free energy delta G coh 。
Step four, microalgae flotation: firstly, 1.0L of microalgae liquid is put into a conical flask, the conical flask is put into a stirring module 7 and is stirred for 2min, then 1.0L of microalgae liquid in the conical flask is put into a flotation tank, then HCL solution or NaOH solution is added into the flotation tank, the PH value of the microalgae liquid in the flotation tank is detected in real time through a PH detector 14, the detected PH value of the microalgae liquid in the flotation tank is sent to a controller 1, the PH value of the microalgae liquid in the flotation tank is 5-10, 45mg/L of floatation agent cetyl trimethyl ammonium bromide is added into the flotation tank, the rotation speed of the flotation tank is regulated to be 800rpm and is stirred for 5-7 min, then the flotation tank is inflated, the detected inflated flow is sent to the controller 1 through an air flowmeter 2, the inflated flow of the flotation tank is 180L/h, and the tail material is obtained through stirring and inflation, and the flotation time is 10-15 min;
in the embodiment, the stirring time of the stirring module 7 in the fifth step is 2min, and in the actual use process, the stirring time of the stirring module 7 can be adjusted within the range of 2 min-4 min according to specific requirements. The addition amount of the hexadecyl trimethyl ammonium bromide of the flotation agent is 45mg/L, and in the actual use process, the addition amount of the hexadecyl trimethyl ammonium bromide of the flotation agent can be adjusted within the range of 45mg/L to 55mg/L according to specific requirements. The rotating speed of the flotation tank is 800rpm, and in the practical use process, the rotating speed of the flotation tank can be adjusted within the range of 800 rpm-1000 rpm according to specific requirements. The aeration flow of the flotation tank is 180L/h, and in the actual use process, the aeration flow of the flotation tank can be adjusted within the range of 180L/h-200L/h according to specific requirements. The flotation time is 10min, and in the actual use process, the flotation time can be adjusted within the range of 10 min-15 min according to specific requirements.
In the embodiment, the conical flask is placed into the stirring module 7 for stirring, so that stirring of microalgae liquid in the conical flask is realized, and microalgae precipitation is avoided; the rotational speed of the flotation tank is regulated to 800rpm and stirred for 5-7 min, so that microalgae liquid in the flotation tank and added floatation agent cetyl trimethyl ammonium bromide are fully and uniformly mixed, and the flotation effect of the microalgae is ensured.
In this embodiment, the air flow rate of the flotation tank is detected in real time by the air flow meter 2, so that the air flow rate of the flotation tank is ensured to meet the requirements, and the flotation effect of microalgae is ensured.
Step five, calculating microalgae flotation efficiency: with the data processing apparatus and according to the formula
Obtaining flotation efficiency W, wherein T represents the weight of the tailings, F represents the weight of 1.0L of microalgae liquid, alpha represents the density of microalgae in 1.0L of microalgae liquid, and beta represents the density of microalgae in the tailings;
in the actual operation process, the density alpha of microalgae in the 1.0L microalgae liquid and the density beta of microalgae in the tailing are detected by adopting a blood cell counting plate.
Step six, obtaining the relation between the flotation efficiency and the free energy of the microalgae surface: in the first step, the PH value of the microalgae solution is p 1 、p 2 、p 3 、...、p n When the free energy of the microalgae surface is respectively obtained as delta G coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn Meanwhile, in the fifth step, the pH value of the microalgae solution in the flotation tank is p 1 、p 2 、p 3 、...、p n Respectively obtain flotation efficiency W 1 、W 2 、W 3 、...、W n The method comprises the steps of carrying out a first treatment on the surface of the Drawing software is called by adopting the data processing equipment to obtain free energy delta G of the microalgae surface cohi On the abscissa, flotation efficiency W i On the ordinate, the free energy DeltaG of the microalgae surface is drawn coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn And flotation efficiency W 1 、W 2 、W 3 、...、W n Corresponding each point, and fitting to obtain the free energy delta G of the microalgae surface cohi And flotation efficiency W i The relation curves and expressions are synchronously displayed through a display 8, wherein the values of i are respectively 1, 2, 3, n and 5 is less than or equal to p 1 ＜p 2 ＜p 3 ＜....＜p n ≤10。
In this embodiment, n=6, p 1 ＝5，p 2 ＝6，p 3 ＝7，p 4 ＝8，p 5 ＝9，p 6 ＝10。
In this embodiment, the microalgae liquid is chlorella liquid, anabaena liquid, rhodococcus liquid, phaeodactylum liquid or dunaliella salina liquid.
In this embodiment, the microalgae solution is further preferably chlorella solution, to obtain the free energy Δg of the chlorella surface cohi And flotation efficiency W i The relationship and expression between them are shown in fig. 3.
Example 3
In this embodiment, unlike embodiment 2, the following is: in this embodiment, the microalgae solution is an anabaena solution, the rotational speed of centrifugation in step 101 is 3000rpm, the time of centrifugation is 10min, the test tube is kept stand for 15min in step 201, the stirring time of the stirring module 7 in step five is 4min, the adding amount of hexadecyl trimethyl ammonium bromide as a flotation agent is 55mg/L, the rotational speed of the flotation tank is 1000rpm, the aeration flow of the flotation tank is 200L/h, and the flotation time is 15min. In this example, the remaining steps and process parameters were the same as in example 2.
In this example, the surface free energy ΔG of anabaena was obtained cohi And flotation efficiency W i The relationship and expression between them are shown in fig. 4.
Example 4
In this embodiment, unlike embodiment 2, the following is: in this embodiment, the microalgae solution is chlorella solution, the rotational speed of centrifugation in step 101 is 2800rpm, the time of centrifugation is 8min, the test tube is kept stand for 8min in step 201, the stirring time of the stirring module 7 in step five is 3min, the adding amount of hexadecyl trimethyl ammonium bromide as a flotation agent is 50mg/L, the rotational speed of the flotation tank is 900rpm, the aeration flow of the flotation tank is 190L/h, and the flotation time is 13min. In this example, the remaining steps and process parameters were the same as in example 2.
In this example, the free energy of the surface of the rhodococcus acidilactici solution was obtainedΔG cohi And flotation efficiency W i The relationship and expression between them are shown in fig. 5.
In conclusion, the method has the advantages of reasonable design, simple and convenient operation and good use effect, obtains the relation between the flotation efficiency and the free energy of the microalgae surface, accurately and reliably predicts the flotation efficiency of the microalgae under different free energies of the surfaces, and provides a basis for rapidly selecting high-efficiency flotation conditions in the microalgae flotation industry.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes made to the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for predicting microalgae flotation efficiency is characterized by comprising the following steps: the method comprises the following steps:
step one, measuring contact angles of microalgae and detection liquid, wherein the measurement process comprises the following steps:
step 101, washing microalgae liquid and regulating pH: washing the microalgae liquid twice by deionized water, adding an HCL solution or a NaOH solution into the washed microalgae liquid, detecting the PH value of the washed microalgae liquid in real time by a PH detector (14), and sending the detected PH value of the washed microalgae liquid to a controller (1) to enable the PH value of the washed microalgae liquid to be 5-10, thus obtaining the microalgae liquid to be treated;
step 102, centrifuging microalgae liquid to be treated: placing the microalgae liquid to be treated obtained in the step 101 into a centrifugal cup containing deionized water, and then placing the centrifugal cup into a centrifugal module (11) for centrifugal treatment to obtain the microalgae liquid to be treated after centrifugal treatment;
step 103: manufacturing of algae lawn: extracting 1-2 mL of the lower microalgae solution of the microalgae solution to be treated after the centrifugation in the step 102 by using a syringe to obtain filtrate; spreading 4-5 drops of the filtrate on a glass slide, and naturally airing the glass slide at normal temperature to prepare an algae lawn;
step 104: detection of microalgae and probe liquid contact angle: the method comprises the steps that detection liquid is dripped on a lawn manufactured in step 103 by adopting the injector, a microalgae detection liquid measurement sample is obtained, when the time set by a timer (6) is reached, a camera (3) collects images of the microalgae detection liquid measurement sample, the collected images of the microalgae detection liquid measurement sample are sent to data processing equipment through an image collection module (4) and a controller (1), the data processing equipment calls a contact angle calculation module to obtain microalgae and detection liquid contact angle theta, the detected microalgae and detection liquid contact angle theta is sent to the controller (1), and the microalgae and detection liquid contact angle theta are synchronously displayed through a display (8);
step two, measuring the Zeta potential of the microalgae, wherein the process is as follows:
step 201, manufacturing a microalgae measurement sample: firstly adding HCL solution or NaOH solution into microalgae solution, detecting the PH value of the microalgae solution in real time by a PH detector (14), sending the detected PH value of the microalgae solution to a controller (1) to enable the PH value of the microalgae solution to be 5-10, obtaining the microalgae solution to be detected, taking 10mL of the microalgae solution to be detected from the microalgae solution to be detected, placing the microalgae solution to be detected into a test tube, standing the test tube for 10-15 min, and then taking supernatant from the test tube to obtain a microalgae measurement sample;
step 202, measuring the Zeta potential of the microalgae: detecting the microalgae measurement sample obtained in the step 201 by adopting a Zeta potential measuring instrument (5), sending the detected microalgae Zeta potential to a controller (1), synchronously displaying the microalgae Zeta potential through a display (8), and selecting a floatation agent cetyl trimethyl ammonium bromide according to the microalgae Zeta potential;
step three, calculating the free energy of the microalgae surface: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy of the detection liquid, wherein +.>
For detecting Van der Waals forces of the fluid, +.>
To detect the electron-withdrawing ability of the liquid, +.>
The electron losing capacity of the detection liquid; then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the free energy delta G of the surface of the microalgae coh ；
Step four, microalgae flotation: firstly, 1.0L of microalgae liquid is put into a conical flask, the conical flask is put into a stirring module (7) and is stirred for 2-4 min, 1.0L of microalgae liquid in the conical flask is put into a flotation tank, then HCL solution or NaOH solution is added into the flotation tank, the PH value of the microalgae liquid in the flotation tank is detected in real time through a PH detector (14), the detected PH value of the microalgae liquid in the flotation tank is sent to a controller (1), the PH value of the microalgae liquid in the flotation tank is 5-10, 45-55 mg/L of cetyltrimethylammonium bromide serving as a flotation agent is added into the flotation tank, the rotation speed of the flotation tank is regulated to be 800-1000 rpm and is stirred for 5-7 min, then the flotation tank is inflated, the inflated flow is detected in real time through an air flowmeter (2), the detected inflated flow is sent to the controller (1), the inflated flow is 180-200L/h, and the tail end of the flotation tank is inflated while stirring, and the inflated flow is obtained for 15min;
step five, calculating microalgae flotation efficiency: with the data processing apparatus and according to the formula
Obtaining flotation efficiency W, wherein T represents the weight of the tailings, F represents the weight of 1.0L of microalgae liquid, alpha represents the density of microalgae in 1.0L of microalgae liquid, and beta represents the density of microalgae in the tailings;
step six, obtaining the relation between the flotation efficiency and the free energy of the microalgae surface: in the first step, the PH value of the microalgae solution is p 1 、p 2 、p 3 、...、p n When the free energy of the microalgae surface is respectively obtained as delta G coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn Meanwhile, in the fifth step, the pH value of the microalgae solution in the flotation tank is p 1 、p 2 、p 3 、...、p n Respectively obtain flotation efficiency W 1 、W 2 、W 3 、...、W n The method comprises the steps of carrying out a first treatment on the surface of the Drawing software is called by adopting the data processing equipment to obtain free energy delta G of the microalgae surface cohi On the abscissa, flotation efficiency W i On the ordinate, the free energy DeltaG of the microalgae surface is drawn coh1 、ΔG coh2 、ΔG coh3 、...、ΔG cohn And flotation efficiency W 1 、W 2 、W 3 、...、W n Corresponding each point, and fitting to obtain the free energy delta G of the microalgae surface cohi And flotation efficiency W i The relation curves and expressions are synchronously displayed through a display (8), wherein the values of i are respectively 1, 2, 3, n, and 5 is less than or equal to p 1 ＜p 2 ＜p 3 ＜....＜p n ≤10。
2. A method according to claim 1, characterized in that: the rotational speed of the centrifugal treatment in the step 101 is 2500 rpm-3000 rpm, and the time of the centrifugal treatment is 5 min-10 min.
3. A method according to claim 1 or 2, characterized in that: the detection liquid comprises deionized water, ethylene glycol and diiodomethane, and the value of l is 1, 2 and 3 respectively;
when the detection liquid is ionized water, glycol and diiodomethane in the step 104, respectively obtaining a contact angle theta 1 of microalgae and ionized water, a contact angle theta 2 of microalgae and glycol and a contact angle theta 3 of microalgae and diiodomethane;
in the third step, the free energy of the microalgae surface is calculated, and the specific process is as follows: first, the data processing apparatus is employed and according to the formula
Obtaining the total surface energy gamma of deionized water 1 Total surface energy gamma of ethylene glycol 2 And diiodomethane surface energy gamma 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>
Van der Waals force of deionized water, +.>
For deionized water to gain electronic ability,/o>
For de-ionized water electron-withdrawing ability->
Van der Waals force of ethylene glycol, +.>
For the electron gain of ethylene glycol, +.>
Is the electron-losing ability of glycol, +.>
Van der Waals force for diiodomethane, < >>
For diiodomethane electron-obtaining ability, +.>
Electron-losing ability of diiodomethane;
then, the data processing apparatus is employed and according to the formula
Obtaining Van der Waals force on the surface of the microalgae
Microalgae surface electron-gaining ability>
And the surface electron-losing ability of microalgae>
Finally, the data processing device is employed and according to the formula
Obtaining the free energy delta G of the surface of the microalgae coh 。
4. A method according to claim 1 or 2, characterized in that: the microalgae liquid is chlorella liquid, anabaena liquid, rhodococcus liquid, phaeodactylum tricornutum liquid or Dunaliella salina liquid.
5. A method according to claim 1 or 2, characterized in that: in step 104, the time set by the timer (6) is 0.5s;
the diameter of the syringe needle is 0.2mm.
6. A microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics used in the method of claim 1, wherein the apparatus comprises: the device comprises a controller (1), a contact angle detection module, a Zeta potential measuring instrument (5) for detecting the Zeta potential of microalgae, and data processing equipment connected with the controller (1), wherein the input end of the controller (1) is connected with an air flow meter (2), a PH detection meter (14) and a timer (6), the output end of the controller (1) is connected with a stirring module (7), a centrifugal module (11) and a display (8), the contact angle detection module comprises a camera (3) and an image acquisition module (4) connected with the output end of the camera (3), and the image acquisition module (4) is connected with the controller (1).
7. The microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics as claimed in claim 6, wherein: the system also comprises a memory (9) and a parameter setting module (10), wherein the memory (9) and the parameter setting module (10) are connected with the controller (1).
8. The microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics as claimed in claim 6 or 7, wherein: the data processing device is a computer (13), and the computer (13) is in bidirectional communication with the controller (1) through a data communication module (12).
9. The microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics as claimed in claim 6 or 7, wherein: the Zeta potential measuring instrument (5) comprises a laser generating device for generating laser and a detection needle for detecting microalgae Zeta potential.
10. The microalgae flotation efficiency prediction apparatus based on microalgae surface characteristics as claimed in claim 8, wherein: the data communication module (12) is an RS232 serial port communication interface circuit or an RS485 serial port communication interface circuit.
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