CN107893064A - The preparation method and applications of the fixed microalgae bead of charcoal polyvinyl alcohol joint - Google Patents
The preparation method and applications of the fixed microalgae bead of charcoal polyvinyl alcohol joint Download PDFInfo
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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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention belongs to microbiological treatment Treating Industrial Wastewater field, more particularly to the preparation method and applications of the microalgae bead of charcoal polyvinyl alcohol joint fixation.The present invention will crush by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain algae powder；Then using algae powder, charcoal and polyvinyl alcohol as raw material, a kind of preparation method of the fixed microalgae bead of charcoal polyvinyl alcohol joint is established, preparation technology is relatively simple, and material therefor is cheap and easy to get, and production cost is low, it is easy to accomplish industrial-scale production.The invention also discloses microalgae bead in the application of absorbing heavy metal ions, can reduce the heavy metal ion content in the industrial wastewater of heavy metal pollution, and adsorption rate is higher, and granular bead is easily separated with solution, is easy to reclaim, and recycling can be achieved.
Description
Technical field
The invention belongs to microbiological treatment Treating Industrial Wastewater field, more particularly to charcoal-polyvinyl alcohol joint to fix
Microalgae bead preparation method and applications.
Background technology
In recent years due to heavy metal pollution caused by the unreasonable processing and discharge of commercial metal waste water, the life to people
Living and ecological environment causes very serious negative effect.Therefore, removing the heavy metal ion in waste water turns into urgently to be resolved hurrily
Thorny problem.Traditional physico-chemical process such as active carbon adsorption, chemical precipitation method zeolite molecular sieve absorption method etc. are located
Waste water is managed, adsorbance is low, removes not exclusively, required costly, and easily causes secondary pollution, so it is low to find new cost
Honest and clean and advantages of good adsorption effect adsorbent turns into the target of processing heavy metal wastewater thereby at present.
In the 1960s, with the development of microalgae biotechnology in world wide, the processing of microalgae biosorption process
Heavy metal wastewater thereby has obtained extensive concern, and it has adsorbance big, and cost is low, the advantages that non-secondary pollution, but due to from
It is small by frond individual, it is difficult to realize the separation of algae and waste water after processing waste water, is restricted in actual applications.
Compared with free algae, immobilized algae has algae cell density height, reaction speed is fast, absorption property is stable, algae
Cell is lost in few, and the advantages that be easy to separate with waste water, there is more wide application prospect in the treatment of waste water.Utilize immobilization
It is to overcome having for the shortcomings of traditional algae sewage disposal system residence time being long, occupation of land is more that this technology, which forms alga system,
Effect approach.
Charcoal is a kind of containing charcoal, stable, height virtue that biomass thermal cracking under anoxic or oxygen free condition obtains
The novel environmental functional material of sweetening treatment, there is larger application potential in terms of the environment of repairing heavy metal pollution.Charcoal day
Right loose structure has stronger absorption affinity to toxic heavy metal, noxious material is fixed on charcoal by adsorbing fixation
On micropore surface, so as to reduce chemism and toxicity of these pollutants in soil, reach repairing polluted soil longer
Purpose.
Compared to charcoal, microalgae is currently used another kind of biological adsorption agent, and heavy metal reparation is carried out using microalgae
Have the advantage that：(1) suction-operated is fast, and the holdup time is short, saves energy consumption；(2) cost is low, it is not necessary to continues organic matter and supplies
Give；(3) heavy metal of recovery is easy to elute, and just recycling can be desorbed with simple chemical reagent；(4) speed of growth is fast, comes
Enrich in source；(5) environmentally friendly, no discarded object produces；(6) surface to volume ratio is big, and adsorption efficiency is high；(7) in high heavy metal concentration and a low huge sum of money
There is good removal effect under category concentration.
And the surface pore of charcoal can provide habitat for microalgae, the surface functional group of charcoal can neutralize microalgae table
The negative electrical charge in face, the repulsion between frustule and carrier is reduced, promotes the secretion of extracellular polymeric, so as to promote to fix frustule
Stability.In addition, the growth of microalgae also results in the surface physics of charcoal, chemical characteristic changes.Microalgae and biology
Charcoal is each advantageous in terms of heavy metal reparation, and from this angle of immobilized microalgae, charcoal is undoubtedly optimal absorption and carried
Body.Using charcoal as carrier, frustule is fixed on biological carbon surface and forms mixed adsorbent, further improves carbon-based immobilization
The adsorption rate and recovery rate of microalgae adsorbent.Such as the patent of invention that application publication number is the A of CN 106076278, one is disclosed
The method that kind charcoal base microalgae compound adsorbent removes removing heavy metals, it is using charcoal as base material, by the way that microalgae is fixed
Compound adsorbent is formed on biological high-area carbon, removing heavy metals can be removed.But charcoal and algae powder are powder, after absorption very
Hardly possible is separated with heavy metal, is recycled difficult.
The content of the invention
Combine the preparation method of fixed microalgae bead it is an object of the invention to provide a kind of charcoal-polyvinyl alcohol,
Preparation technology is relatively simple, and material therefor is cheap and easy to get, and production cost is low, it is easy to accomplish industrial-scale production.
Another object of the present invention is to provide a kind of charcoal-fixed microalgae bead of polyvinyl alcohol joint in absorption weight
Application in terms of metal ion, the heavy metal ion content in the industrial wastewater of heavy metal pollution can be reduced, adsorption rate is higher, and
Granular bead is easily separated with solution, is easy to reclaim, and recycling can be achieved.
To achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, comprises the following steps：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 80-100 mesh；
Step 2：Desert silk algae powder is mixed with ultra-pure water, 5~10min of magnetic agitation, then is ground with glass blender,
Obtain uniform desert silk algae algae suspension；
Step 3：Charcoal is added into desert silk algae algae suspension, vibration mixes 2h, obtains the first mixed liquor；The desert silk
The mass ratio of algae powder and charcoal is 1：(1~3)；
Step 4：According to volume ratio it is 1 by the first mixed liquor in step 3 and poly-vinyl alcohol solution：1, to having cooled to room temperature
The first mixed liquor is added in poly-vinyl alcohol solution, the second mixed liquor is obtained, magnetic agitation to bubble-free, the second mixed liquor is instilled
In saturation boric acid solution, cold curing 6-12h, the microalgae bead for being fixed, microalgae bead is cleaned to washing lotion with ultra-pure water
In neutrality；
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
Further, the algae of desert silk described in step 1 is the tool micro- sheath algae of sheath.
Further, the particle diameter of charcoal described in step 3 is 100 mesh.
Further, when second mixed liquor is instilled in saturation boric acid solution described in step 4, operating instrument is apart from saturation
The height of boric acid solution liquid level is not less than 10cm.
Further, the polyoxyethylene octyl that concentration is 50mmol/L is contained in saturation boric acid solution described in step 4
Phenol ether, the pH value of saturation boric acid solution is 6.7.
The present invention also provides a kind of preparation method system based on above-mentioned charcoal-fixed microalgae bead of polyvinyl alcohol joint
Application of the standby charcoal-fixed microalgae bead of polyvinyl alcohol joint in absorbing heavy metal ions.
Further, above-mentioned application comprises the following steps：It is small that microalgae is added into the heavy metal ion solution of manual simulation
Ball, it is placed in 1~24h in shaking table；The addition quality of the microalgae bead for manual simulation heavy metal ion liquor capacity 1~
4.5%.
Compared with prior art, the beneficial effects of the present invention are：
1. the present invention using charcoal-polyvinyl alcohol carries out joint fixation to microalgae, both by the charcoal all with adsorptivity with
Desert silk algae combines, and is prepared into granular microalgae bead, enhances mechanical performance and the absorption of immobilization material again
Performance, preparation technology is relatively simple, and material therefor is cheap and easy to get, and production cost is low, it is easy to accomplish industrial-scale production.
2. Cu in charcoal of the present invention-fixed microalgae bead heavy metal solion of polyvinyl alcohol joint2+、Pb2+、
Cr6+And Cd2+Adsorption effect it is obvious, micro- algae powder, charcoal powder or micro- algae powder+biological powdered carbon two with single component
Person's mixture is compared, and adsorption rate is significantly improved, and after heavy metal solion is adsorbed, granular bead is easy
Separated with heavy metal ion solution, be easy to reclaim, recycling can be achieved.
Embodiment
Following examples are used to illustrate the present invention, but are not used to limit protection scope of the present invention.It is unless otherwise specified, real
Apply the conventional meanses that technological means used is well known to those skilled in the art in example.Test method in following embodiments, such as
It is conventional method without special instruction.
Charcoal be wheat stalk or peanut shell under conditions of anoxic, be prepared through 450~700 DEG C of Pintsch process
A kind of indissoluble, stable, height aromatization, rich in carbon solid matter.After the completion of prepared by charcoal, air-dry, warp
100 mesh screens, preserved at aeration-drying, it is standby.
The desert silk algae that the present invention selects is the tool micro- sheath algae of sheath (Microcoleus vaginatus), but the present invention utilizes
Charcoal-fixed microalgae of polyvinyl alcohol joint obtains the preparation method of microalgae bead, is not limited in the fixed tool micro- sheath algae of sheath, also
Suitable for other desert silk algaes.It is that one of most commonly used desert algae species are distributed in desert soil to have the micro- sheath algae of sheath, and it is given birth to
Object amount is sometime up to more than the 95% of edaphon total amount, has growth vigor and characterization of adsorption, as filament is flourishing, extracellular
Polysaccharide secretory volume is big.The artificial pilot scale culture of desert silk algae is carried out first.Using BG-11 fluid nutrient mediums as culture medium
Matter, desert silk algae is expanded into culture by I grade of algae kind culture, II grade of algae kind culture and III grade of algae kind respectively and carries out algae kind step by step
Spread cultivation, the three-level algae kind that will be enlarged by culture is transferred to bioreactor or racetrack circulatory pool progress pilot scale culture.With
In the cultures at different levels of upper desert silk algae, condition of culture is：28-35 DEG C of temperature, light intensity 3000Lux-4000Lux, continuous ventilation training
Support 15-30 days, after testing after, frond biomass reaches Chlorophyll-a Content in nutrient solution when be 8~10 μ g/mL, collection frond,
Air-dry in its natural state, obtain desert silk algae algae piece, save backup.
The component of above-mentioned BG-11 fluid nutrient mediums is as follows (to be often upgraded to example)：1.5g sodium nitrate, 0.04g three water phosphorus
Sour hydrogen dipotassium, 0.07g epsom salt, 0.036g calcium chloride dihydrate, 0.006g citric acid, 0.006g ironic citrate
Ammonium, 0.001g disodium EDTA (EDTA), 0.02g sodium carbonate, micro- A5 liquid 1mL；Wherein A5 liquid group
Divide (to be often upgraded to example)：2.86g boric acid, 0.039g Sodium Molybdate Dihydrate, 0.222g white vitriol, 0.074g five water
A water manganese chloride, the 0.049g cobalt nitrate hexahydrate of copper sulphate, 1.18g.
In following examples used syringe needle specification be 18G (internal diameter 0.86mm, external diameter 1.26mm),
20G (internal diameter 0.6mm, external diameter 0.9mm) and disposable needle tubing (20ml) original-pack syringe needle.
Embodiment one
A kind of preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, comprises the following steps：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 80 mesh.
Step 2：0.5g desert silk algae powders are mixed with 50ml ultra-pure waters, magnetic agitation 5min, then use glass blender
It is ground, obtains uniform desert silk algae algae suspension.Single desert silk algae frustule is obtained during grinding as far as possible, exposure is more
Binding site, to increase the relative surface area of desert silk algae frustule.
Step 3：1.5g charcoals are added into 50ml desert silk algae algae suspension, vibration mixes 2h with by desert silk algae algae
Cell is sufficiently secured within charcoal, so as to obtain the first mixed liquor.
Step 4：Polyvinyl alcohol grind processing so that polyvinyl alcohol is easier to melt before heating is melted, with dry mill
Change.6g polyvinyl alcohol is added into 50ml ultra-pure waters, heated on infrared heating furnace, polyvinyl alcohol is melted to obtain polyvinyl alcohol molten
Liquid, it is cooled to room temperature.Configure in saturation boric acid solution containing the polyoxyethylene octane alkylphenol ether (OP- that concentration is 50mmol/L
10), the pH value of saturation boric acid solution is 6.7.
The addition mixed liquors of 50ml first in the poly-vinyl alcohol solution of room temperature are had cooled to 50ml, obtain the second mixed liquor,
Wherein the concentration of polyvinyl alcohol is 6%, magnetic agitation to bubble-free.
The second mixed liquor is instilled in 400ml saturation boric acid solutions with syringe needle model 20G syringe, injected during operation
Device needle point is 12cm, cold curing 6h apart from the height of saturation boric acid solution liquid level, and it is small to obtain the microalgae that particle diameter is 2mm immobilizations
Ball, microalgae bead is cleaned to washing lotion in neutrality with ultra-pure water, microalgae bead and saturation boric acid solution are separated.
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
Embodiment two
A kind of preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, comprises the following steps：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 100 mesh.
Step 2：1g desert silk algae powders are mixed with 50ml ultra-pure waters, magnetic agitation 8min, then entered with glass blender
Row grinding, obtains uniform desert silk algae algae suspension.Single desert silk algae frustule is obtained during grinding as far as possible, exposure is more
Binding site, to increase the relative surface area of desert silk algae frustule.
Step 3：3g charcoals are added into 50ml desert silk algae algae suspension, vibration mixes 2h so that desert silk algae algae is thin
Born of the same parents are sufficiently secured within charcoal, so as to obtain the first mixed liquor.
Step 4：Polyvinyl alcohol grind processing so that polyvinyl alcohol is easier to melt before heating is melted, with dry mill
Change.7g polyvinyl alcohol is added into 50ml ultra-pure waters, heated on infrared heating furnace, polyvinyl alcohol is melted to obtain polyvinyl alcohol molten
Liquid, it is cooled to room temperature.Configure in saturation boric acid solution containing the polyoxyethylene octane alkylphenol ether (OP- that concentration is 50mmol/L
10), the pH value of saturation boric acid solution is 6.7.
The addition mixed liquors of 50ml first in the poly-vinyl alcohol solution of room temperature are had cooled to 50ml, obtain the second mixed liquor,
Wherein the concentration of polyvinyl alcohol is 7%, magnetic agitation to bubble-free.
The second mixed liquor is instilled in 400ml saturation boric acid solutions with syringe needle model 18G syringe, injected during operation
Device needle point is 12cm, cold curing 8h apart from the height of saturation boric acid solution liquid level, and it is small to obtain the microalgae that particle diameter is 3mm immobilizations
Ball, microalgae bead is cleaned to washing lotion in neutrality with ultra-pure water, microalgae bead and saturation boric acid solution are separated.
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
Embodiment three
A kind of preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, comprises the following steps：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 80 mesh.
Step 2：2g desert silk algae powders are mixed with 50ml ultra-pure waters, magnetic agitation 10min, then entered with glass blender
Row grinding, obtains uniform desert silk algae algae suspension.Single desert silk algae frustule is obtained during grinding as far as possible, exposure is more
Binding site, to increase the relative surface area of desert silk algae frustule.
Step 3：6g charcoals are added into 50ml desert silk algae algae suspension, vibration mixes 2h so that desert silk algae algae is thin
Born of the same parents are sufficiently secured within charcoal, so as to obtain the first mixed liquor.
Step 4：Polyvinyl alcohol grind processing so that polyvinyl alcohol is easier to melt before heating is melted, with dry mill
Change.8g polyvinyl alcohol is added into 50ml ultra-pure waters, heated on infrared heating furnace, polyvinyl alcohol is melted to obtain polyvinyl alcohol molten
Liquid, it is cooled to room temperature.Configure in saturation boric acid solution containing the polyoxyethylene octane alkylphenol ether (OP- that concentration is 50mmol/L
10), the pH value of saturation boric acid solution is 6.7.
The addition mixed liquors of 50ml first in the poly-vinyl alcohol solution of room temperature are had cooled to 50ml, obtain the second mixed liquor,
Wherein the concentration of polyvinyl alcohol is 8%, magnetic agitation to bubble-free.
The second mixed liquor is instilled in 400ml saturation boric acid solutions with disposable needle tubing (20ml), syringe needle during operation
Point is 15cm, cold curing 12h apart from the height of saturation boric acid solution liquid level, obtains the microalgae bead that particle diameter is 4mm immobilizations,
Microalgae bead is cleaned to washing lotion in neutrality with ultra-pure water, and microalgae bead and saturation boric acid solution are separated.
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
Example IV
A kind of preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, comprises the following steps：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 80 mesh.
Step 2：3g desert silk algae powders are mixed with 50ml ultra-pure waters, magnetic agitation 10min, then entered with glass blender
Row grinding, obtains uniform desert silk algae algae suspension.Single desert silk algae frustule is obtained during grinding as far as possible, exposure is more
Binding site, to increase the relative surface area of desert silk algae frustule.
Step 3：3g charcoals are added into 50ml desert silk algae algae suspension, vibration mixes 2h so that desert silk algae algae is thin
Born of the same parents are sufficiently secured within charcoal, so as to obtain the first mixed liquor.
Step 4：Polyvinyl alcohol grind processing so that polyvinyl alcohol is easier to melt before heating is melted, with dry mill
Change.7g polyvinyl alcohol is added into 50ml ultra-pure waters, heated on infrared heating furnace, polyvinyl alcohol is melted to obtain polyvinyl alcohol molten
Liquid, it is cooled to room temperature.Configure in saturation boric acid solution containing the polyoxyethylene octane alkylphenol ether (OP- that concentration is 50mmol/L
10), the pH value of saturation boric acid solution is 6.7.
The addition mixed liquors of 50ml first in the poly-vinyl alcohol solution of room temperature are had cooled to 50ml, obtain the second mixed liquor,
Wherein the concentration of polyvinyl alcohol is 7%, magnetic agitation to bubble-free.
The second mixed liquor is instilled in 400ml saturation boric acid solutions with syringe needle model 18G syringe, injected during operation
Device needle point is 15cm, cold curing 8h apart from the height of saturation boric acid solution liquid level, and it is small to obtain the microalgae that particle diameter is 3mm immobilizations
Ball, microalgae bead is cleaned to washing lotion in neutrality with ultra-pure water, microalgae bead and saturation boric acid solution are separated.
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
Embodiment five
Configuration concentration is the heavy metal ion solution of 300mg/L manual simulation, and the heavy metal ion of wherein 1L manual simulations is molten
Cupric sulfate pentahydrate containing 1.17g in liquid, 0.55g lead acetate, 1.7g potassium bichromate and 0.61g chromium chloride, then manually
Cu in the heavy metal ion solution of simulation2+、Pb2+、Cr6+And Cd2+Initial concentration be 0.3g/L.
The microalgae bead for using particle diameter prepared by embodiment three to be air-dried for 4mm, to the heavy metal ion of 20mL manual simulations
0.6g microalgae beads are added in solution, are placed in 6h in shaking table.3 repetitions are done every time, adsorption rate is averaged.Microalgae bead pair
Cu2+、Pb2+、Cr6+、Cd2+Four heavy metal species ions are adsorbed, and with traditional micro- algae powder, charcoal powder and microalgae algae
Powder+both biological powdered carbons mixture carries out heavy metal ion adsorbed effect and compares (the microalgae algae contained in 0.6g microalgae beads
Powder amount or charcoal amount are 0.08g), with four in the heavy metal ion solution after the measure absorption of A3 types atomic absorption spectrophotometer
The final concentration of heavy metal species, adsorption rate is calculated, as a result as shown in table 1.
The adsorption rate of the traditional micro- algae powder of table 1, charcoal powder and microalgae bead heavy metal ion
As can be seen from Table 1, micro- algae powder with single component, charcoal powder or micro- algae powder+both biological powdered carbons
Mixture is compared, and the adsorption effect of charcoal-fixed microalgae bead heavy metal ion of polyvinyl alcohol joint is substantially preferable, and
Microalgae bead is simple with the separation of heavy metal ion solution after absorption terminates, easy to operate.
Embodiment six
The present embodiment and embodiment five are essentially identical, and difference is：Use what particle diameter prepared by embodiment one air-dried for 2mm
Microalgae bead, 0.4g microalgae beads are added into the heavy metal ion solution of 20mL manual simulations, are placed in 3h in shaking table.With A3 types
The final concentration of four heavy metal species, calculates adsorption rate in heavy metal ion solution after atomic absorption spectrophotometer measure absorption,
Microalgae bead is to Cu2+、Pb2+、Cr6+、Cd2+The adsorption rate of four heavy metal species ions is respectively 89.16%, 92.7%, 91.34%,
78.29%.
Embodiment seven
The present embodiment and embodiment five are essentially identical, and difference is：Use what particle diameter prepared by example IV air-dried for 3mm
Microalgae bead, 0.4g microalgae beads are added into the heavy metal ion solution of 20mL manual simulations, are placed in 5h in shaking table.With A3 types
The final concentration of four heavy metal species, calculates adsorption rate in heavy metal ion solution after atomic absorption spectrophotometer measure absorption,
Microalgae bead is to Cu2+、Pb2+、Cr6+、Cd2+The adsorption rate of four heavy metal species ions is respectively 98.97%, 95.35%,
92.78%th, 83.78%.
Embodiment eight
The present embodiment and embodiment five are essentially identical, and difference is：Use what particle diameter prepared by embodiment three air-dried for 4mm
Microalgae bead, be separately added into the heavy metal ion solution of 20mL manual simulations 0.2g, 0.4g, 0.5g, 0.6g, 0.8g and
0.9g microalgae bead, is placed in 6h in shaking table.3 repetitions are done every time, adsorption rate is averaged.Microalgae bead is to Cu2+、Pb2+、
Cr6+、Cd2+Four heavy metal species ions are adsorbed, with the heavy metal ion after the measure absorption of A3 types atomic absorption spectrophotometer
The final concentration of four heavy metal species in solution, adsorption rate is calculated, as a result as shown in table 2.
The adsorption rate of microalgae bead heavy metal ion under 2 different dosages of table
As can be seen from Table 2, microalgae bead all increases to the adsorption rate of four heavy metal species ions with the increase of dosage
By force, because in the case where adsorbent dosage is less, functional group's total amount of adsorbent is less, and microalgae bead can not provide
Enough adsorption sites, thus it is very low to the adsorption rate of four heavy metal species ions.But with increasing for dosage, its functional group
Total amount also increases, and adsorption rate will be improved accordingly.But as the dosage of microalgae bead continues to increase, adsorption rate increase is slow,
This is due to the effect that interferes between electrostatic interaction and reactive group, prevents heavy metal ion from being combined with adsorption site, causes
The adsorption rate increase of immobilized spherule heavy metal is slow.
Embodiment nine
The present embodiment and embodiment five are essentially identical, and difference is：Use what particle diameter prepared by embodiment three air-dried for 4mm
Microalgae bead, 0.6g microalgae bead is separately added into the heavy metal ion solution of 20mL manual simulations, is placed in shaking table and divides
5min, 15min, 30min, 1h, 2h, 4h, 6h, 8h, 12h and 24h are not shaken.3 repetitions are done every time, adsorption rate is averaged.It is micro-
Algae bead is to Cu2+、Pb2+、Cr6+、Cd2+Four heavy metal species ions are adsorbed, and are determined and inhaled with A3 types atomic absorption spectrophotometer
The final concentration of four heavy metal species in attached heavy metal ion solution, adsorption rate is calculated, as a result as shown in table 3.
The adsorption rate of microalgae bead heavy metal ion under 3 different adsorption times of table
As can be seen from Table 3, the adsorption process of microalgae bead heavy metal ion is divided into 2 stages：First stage is
Physical absorption, to Cu2+、Pb2+、Cd2+Absorption all quickly carried out in preceding 8h, adsorption rate has respectively reached 90.74%, 96.55%
With 82.3%；To Cr6+Absorption quickly carried out in preceding 6h, adsorption rate has reached 89.71%.It is molten that this is due to that adsorbent is present in
A large amount of adsorption sites are provided for heavy metal in liquid, enhance ion exchange.Second stage is chemisorbed process, 8-
To Cu in 24h2+、Pb2+、Cd2+With in 6-24h to Cr6+Adsorption rate slowly increase over time, this stage master
If adsorbing the process that the metal ion on frustule surface is further transferred to cell interior, this step is carried out very slow.
Embodiment described above, simply presently preferred embodiments of the present invention, only to explain the present invention, is not limited
The scope of the present invention processed, to those of ordinary skill in the art, certainly can be according to skill disclosed in this specification
Art content, make other embodiments easily by way of replacing or changing, thus it is all in principle and technique bar of the invention
Changes and improvements that part is done etc., it all should be included in scope of the present invention patent.
Claims (7)
1. the preparation method of a kind of charcoal-fixed microalgae bead of polyvinyl alcohol joint, it is characterised in that including following step
Suddenly：
Step 1：It will be crushed by artificial pilot scale culture, air-dried obtained desert silk algae algae piece, sieving, obtain desert silk algae algae
Powder, desert silk algae powder fineness are 80-100 mesh；
Step 2：Desert silk algae powder is mixed with ultra-pure water, 5 ~ 10min of magnetic agitation, then is ground with glass blender,
Obtain uniform desert silk algae algae suspension；
Step 3：Charcoal is added into desert silk algae algae suspension, vibration mixes 2h, obtains the first mixed liquor；The desert silk
The mass ratio of algae powder and charcoal is 1：（1~3）；
Step 4：According to volume ratio it is 1 by the first mixed liquor in step 3 and poly-vinyl alcohol solution：1, to having cooled to room temperature
The first mixed liquor is added in poly-vinyl alcohol solution, the second mixed liquor is obtained, magnetic agitation to bubble-free, the second mixed liquor is instilled
In saturation boric acid solution, cold curing 6-12h, the microalgae bead for being fixed, microalgae bead is cleaned to washing lotion with ultra-pure water
In neutrality；
Step 5：The microalgae bead cleaned is positioned in culture dish, room temperature air-dries, standby.
2. the preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, its feature exist according to claim 1
In the algae of desert silk described in step 1 is the tool micro- sheath algae of sheath.
3. the preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, its feature exist according to claim 1
In the particle diameter of charcoal described in step 3 is 100 mesh.
4. the preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, its feature exist according to claim 1
In when second mixed liquor is instilled in saturation boric acid solution described in step 4, operating instrument is apart from saturation boric acid solution liquid level
Highly it is not less than 10cm.
5. the preparation method of charcoal-fixed microalgae bead of polyvinyl alcohol joint, its feature exist according to claim 1
In, in saturation boric acid solution described in step 4 contain concentration be 50mmol/L polyoxyethylene octane alkylphenol ether, saturation boric acid
The pH value of solution is 6.7.
6. prepared by the preparation method of any one of claim 1 ~ 5 charcoal-fixed microalgae bead of polyvinyl alcohol joint
Application of the charcoal-fixed microalgae bead of polyvinyl alcohol joint in absorbing heavy metal ions.
7. charcoal-fixed microalgae bead of polyvinyl alcohol joint is in absorbing heavy metal ions according to claim 6
Application, it is characterised in that comprise the following steps：Microalgae bead is added into the heavy metal ion solution of manual simulation, is placed in
1 ~ 24h in shaking table；The addition quality of the microalgae bead is the 1 ~ 4.5% of the heavy metal ion liquor capacity of manual simulation.
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