CN1171805C - Mycelium surface coated biologic adsorbent and preparing process thereof - Google Patents
Mycelium surface coated biologic adsorbent and preparing process thereof Download PDFInfo
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- CN1171805C CN1171805C CNB021310319A CN02131031A CN1171805C CN 1171805 C CN1171805 C CN 1171805C CN B021310319 A CNB021310319 A CN B021310319A CN 02131031 A CN02131031 A CN 02131031A CN 1171805 C CN1171805 C CN 1171805C
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Abstract
The present invention relates to a mycelium surface coating biologic adsorbing agent and a preparation method thereof, particularly to a biologic adsorbing agent with coating layers outside mycelia and a preparation method thereof. The mycelia are citric acid bacteria, saccharomycete, penicillia or fungi, and the coating layers are made of glucan, chitosan or chitosan derivatives. The particle diameter of each mycelium is less than or equal to 3mm, and the consumption ratio of the coating layers to the mycelia is from 1 to 0.01 g/g. In the present invention, the surface coating biologic adsorbing agent or a surface coating blotting biologic adsorbing agent is obtained with a coating method or a method of blotting treatment and coating which are carried out simultaneously. The present invention is suitable for the treatment of wastewater having a heavy metal ion content of 5 to 2000 ppm, and the pH value of the wastewater is within the range of 2 to 11. The biologic adsorbing agent provided by the present invention has the advantage of low cost, the adsorption capacity of the biologic adsorbing agent can reach 30 to 100 mg/g, and the biologic adsorbing agent can be repeatedly used for 20 times. The biologic adsorbing agent is mainly used for treating dye wastewater, metallurgical wastewater, tanning wastewater, phenol containing wastewater, etc.
Description
Technical field
The present invention relates to a kind of biological adsorption agent that coating layer is arranged outside mycelium and preparation method thereof, mycelium is citric acid fungus, yeast, Penicillium notatum or fungi, and coating layer material is crosslinked dextran, chitosan or chitosan derivatives.This biological adsorption agent is used to handle heavy metal ion-containing waste water.
Background technology
Contain contents of many kinds of heavy metal ion in electroplating wastewater, waste water from dyestuff, leather-making waste water, metallurgical waste water, the pollution problem of these waste water more and more comes into one's own.At present, this class is contained contents of many kinds of heavy metal ion waste water treatment process commonly used method of chemical treatment, ion exchange method, adsorption method of separation, membrane separation process and microbial method etc. are arranged, when these methods contain high density heavy metal ion solution in processing, effect is better, but when containing the micro heavy ion, processing all has certain defective, as complex process, the high or generation secondary pollution problems of cost.Seeking efficient cheap heavy metal ion water conditioner becomes the problem of urgent solution.Utilize biological adsorption agent to handle heavy metal ion-containing waste water and cause the very big interest of people.
At present, China is annual to produce a large amount of discarded mycelium, and these discarded mycelium have only on a small quantity and are used as animal-feed, and the overwhelming majority is abandoned, thus contaminate environment.Discover that mycelium can effectively remove the heavy metal ion in the waste water, mycelium is done industrial water conditioner, comprehensive utilization and environment protection from resource have great importance.Directly adopt mycelium to cook water conditioner, the too Xiao Yi fragmentation of its physical strength, the too low 20mg/g that reaches at most of loading capacity.The physical strength that adopts embedding or immobilized method to improve sorbent material is also arranged at present, but this method complex process, the cost height, loading capacity reduces, and can't promote the use of in water treatment.Extract chitosan and can be used as water conditioner from shrimp shell, crab shell or mycelium, can effectively handle heavy metal ion-containing waste water, have the loading capacity height, the selectivity height only has adsorption to heavy metal ion, and loading capacity is generally at 40～100mg/g.But directly make water conditioner with chitosan, cost is too high, and is easy to run off in acidic solution, is difficult to reclaim.Many at present employing chitosan derivatives or cross-linked chitosan are cooked water conditioner.Chitosan derivatives, as grafting carboxymethyl chitosan glycopolymers, it is to Pd
2+And Cd
2+Has bigger loading capacity; Cross-linked chitosan phendioxin 5-hat-5 ethers and cross-linked chitosan phendioxin 8-hat-6 ethers are to Ag
+, Pb
2+, Cd
2+Deng higher absorption property and selectivity are arranged.The loading capacity of the chitosan resin after crosslinked has certain decline, but swelling not do not run off, and physical strength is good, and is reusable.It is also effective especially that crosslinked N-cm-chitosan is removed metal ion, as deleterious Pb in the no carrying agent radioelement Co-60 in the nuke rubbish, the tap water
2+And Cd
2+And the Mn of big concentration
2+The spent glycol bisglycidyl ether carries out crosslinked to chitosan, the cross-linked resin of gained is to Cu
2+Ion has the good adsorption effect, but compares with uncrosslinked chitosan, and sequestering power descends.Chitin, chitosan and derivative thereof have nontoxic and good absorption property.But chitosan and derivative thereof cost an arm and a leg, thereby have limited applying in Treatment of Industrial Water owing to complicated process of preparation.
The trace method is that material is adopted in advance in conjunction with heavy metal ion, flush away after the embedding, thus stay the trace of heavy metal ion.This method has been applied in the preparation of spherical shell polysaccharide resins.At " spherical Ni
2+The research of template chitosan resin absorption property transitivity " (the 15th the 1st phase of volume of people's " high chemical engineering journal " such as He Xiaojin) reported and used Ni
2+Trace solion, epoxy chloropropane and ethylene glycol bis shrink glycidyl ethers are that linking agent prepares the spherical shell polysaccharide resins.Its preparation method is chitosan to be dissolved in contain NiSO
4.6H
2In the acetic acid solution of O, through granulation formation in solidifying agent alkali lye, through washing, add that linking agent is crosslinked, washing, the desorb of strippant hydrochloric acid, washing, obtain the crosslinked chitosan resin handled through trace with regenerator sig water and washing again.This resin is to Ni
2+, Cu
2+, Zn
2+Have selectivity, and handle without trace relatively, its adsorptive capacity improves 2 times.It is still higher to recycle 10 loading capacities.
Summary of the invention
Mycelium surface coated biologic adsorbent of the present invention and preparation method thereof has proposed a kind ofly can improve the heavy metal ion adsorbed capacity of waste water, water conditioner that reduces production costs and preparation method thereof.
Technical scheme of the present invention is that mycelium surface coated biologic adsorbent is made core material by mycelium, one deck coating layer is arranged outside mycelium, mycelium is citric acid fungus, yeast, Penicillium notatum or fungi, coating layer material is crosslinked dextran, chitosan or chitosan derivatives, mycelium particle diameter≤3mm, coating layer and mycelial amount ratio are 1～0.01g/g.
The chitosan derivatives that the present invention is used, for example: cm-chitosan, N-cm-chitosan, grafting cm-chitosan, chitosan phendioxin 5-hat-5 ethers or chitosan phendioxin 8-hat-6 ethers.
The preparation method's of mycelium surface coated biologic adsorbent of the present invention operation steps is that coating layer material is dissolved in the acid, sour and mycelial amount ratio is 3～20ml/g, mix with mycelium then through the particle diameter≤3mm of fragmentation, adding linking agent again mixed crosslinked 0.5～24 hour down at 10～80 ℃, the add-on of linking agent and mycelial amount ratio are 0.01～10ml/g, crosslinked after filtration washing, add solidifying agent alkali lye, the concentration of solidifying agent is 0.5%～20%, the add-on of solidifying agent and mycelial amount ratio are 10～50ml/g, and drying obtains surface coated biologic adsorbent again.
The present invention also proposes to increase the trace treatment technology on above-mentioned surface coated biologic adsorbent preparation method's basis, operation steps is to be dissolved in the acid back at coating layer material to add the trace solion, trace solion concentration is 20～10000mg/L, trace solion and coating layer material amount ratio are 5～50ml/g, add strippant behind crosslinked, filtration washing, strippant concentration is 0.01～0.5mol/L; Strippant and mycelial amount ratio are 10～50ml/g; Filtration washing adds regenerator once more, and regenerator concentration is 0.05～1mol/L, and regenerator and mycelial amount ratio are 10～50ml/g; Drying obtains the surface and coats the trace biological adsorption agent.
Employed in the present invention acid is organic acid or mineral acid, for example: acetate, oxalic acid, hydrochloric acid, sulfuric acid or nitric acid.
Employed in the present invention linking agent is ethylene glycol bis shrink glycidyl ethers, glutaraldehyde, formaldehyde, epoxy chloropropane, vulcabond or ethylene glycol bis glycidyl ether.
Employed in the present invention solidifying agent alkali lye is sodium hydroxide, ammoniacal liquor, tripoly phosphate sodium STPP or sodium bicarbonate.
Trace processing in the present invention is that used trace solion is nickel, chromium, copper, silver, zinc or cadmium salt soln.Strippant is hydrochloric acid, nitric acid, sulfuric acid, acetate or sequestrant, and sequestrant is iminodiethanoic acid, ether azoles or disodium edta (EDTA).Regenerator is sodium hydroxide, sodium bicarbonate, yellow soda ash or ammoniacal liquor.
Mycelium of the present invention is to handle the mycelium of removing protein and nucleic acid through ordinary method.These mycelium are knownly can adsorb heavy metal ions in wastewater.For the specific surface area that increases sorbent material and be convenient to coat, need carry out break process to mycelium.Mycelium is rounded substantially through coating processing back shape, and specific surface area is big like this, and the intensity height uses pressure drop little in packing tower.
The preparation method of the biological adsorption agent that proposes with the present invention can obtain surface coated biologic adsorbent.The preparation method of the biological adsorption agent that proposes with the present invention can also obtain the surface and coat the trace biological adsorption agent.Biological adsorption agent of the present invention is all higher through trace processing loading capacity and selectivity, can be used for the occasion of some particular requirements.
Coating layer material of the present invention is the organic polymer material high to heavy metal ion adsorbed capacity, sorbent material provided by the invention has only coated the material that Adsorption of Heavy Metal Ions is capacious, physical strength is high on the surface of sorbent material, these materials have good associativity to the core material that is coated, even if coating layer has crack defect or service failure, mycelium still can play adsorption, also is unlikely to simultaneously to use because of the low and broken influence of intensity.The coating layer material intensity height that biological adsorption agent of the present invention adopted, acid and alkali-resistance, loading capacity is big, the selectivity height.Though the coating layer material cost is higher, owing to, like this, both can improve the water conditioner integral intensity, increase access times only in the effective surface use of sorbent material, can reduce the consumption of coating layer material simultaneously, thereby reduce cost.
When preparation of adsorbent of the present invention is carried out crosslinking Treatment in the coating process, use linking agent can reduce the sum of organic polymer film surface and the effective group of metal ion bonded, thereby reduce the loading capacity of water conditioner.Handle through surface molecule print, adopt in advance in conjunction with heavy metal ion, flush away after the embedding, thus stay the trace of heavy metal ion, effectively protect the active group in the resin.Metal ion trace content is high more in the resin, and the active group protection is many more, and loading capacity is big more, can improve the selectivity of the metal ion similar to the trace ionic structure simultaneously.Adopt diluted acid as strippant, increase the repeated use number of times of water conditioner, but diluted acid is as strippant, excessive H
+Ion can change the price of organic polymer group, reduces the adsorptive power to heavy metal ion.Therefore must regenerate after the water conditioner desorb, the neutrality that neutralizes is to remove unnecessary H
+Ion.After the surface molecule print processing, can improve the selectivity and the loading capacity of water conditioner.
Used can adopt when mycelium mixes with coating layer material fluidized-bed, agitator or the rotating bed of the present invention coats.For example, fluidisation coats: feed nitrogen or air, operating gas velocity 0.1～20m/s coats time 0.5h～12h; Stir and coat: 20～200 rev/mins of rotating speeds, 10～80 ℃ of temperature; Rotating bed coats: 20～200 rev/mins, and 10～80 ℃ of temperature.
Adopt the prepared water conditioner of the present invention, be applicable to the content 5～2000ppm of heavy metal ion, pH is the wastewater treatment of 2～11 scopes.The prepared water conditioner cost of the present invention is low, and loading capacity can reach 30～100mg/g, can repeatedly use to reach that loading capacity does not obviously go down more than 10 times yet, even use and reach 20 times and also can continue to use.Be mainly used in the improvement of waste water from dyestuff, metallurgical waste water, leather-making waste water, phenolic wastewater etc.Selected core material mycelium and coating layer material dextran, chitosan and derivative thereof all are biomaterials, can biological degradation, can not produce secondary pollution, and can play the comprehensive utilization of resource, can play the effect of environment protection again.
Embodiment
The measuring method of loading capacity of the present invention is as follows: the 0.15g sorbent material is added in the solution of 50ml metal ion, after the room temperature vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belong to ionic concn, calculate loading capacity according to following formula.
Q＝(Co-Ce)V/W(mg/g)
Wherein: Q-loading capacity (mg/g); Concentration of heavy metal ion (mg/L) before the Co-absorption; The concentration (mg/L) of Ce-absorption back heavy metal ion; W-sorbent material dry weight (g); V-liquor capacity (L).
Embodiment 1
Get in the acetic acid aqueous solution that dextran 0.5g is dissolved in 10ml, 0.5M, add 0.5g citric acid mycelia, mycelium through pulverize, sieving obtains the mycelium of particle diameter≤0.5mm, coats with fluidized-bed, operating gas velocity 20m/s coats time 6h.Add the 5ml epoxy chloropropane and make linking agent, 40 ℃ of crosslinking temperatures, crosslinking time 24 hours.Filtration, adds 25ml, 0.5%NaOH and makees solidifying agent after neutrality with deionized water wash, behind the curing 1h, filters with deionized water wash and arrives neutrality, and drying obtains dried resin and is surface coated biologic adsorbent.Get 0.15g dried resin and 50ml Ni
2SO
4The aqueous solution joins in the Erlenmeyer flask of 150ml, at room temperature, after rotating speed 150dyn/m swings 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Loading capacity be 55mg/g.Show that by experimental result this sorbent material can use in the scope of pH=2～11 broads; At Ni
2+Concentration is under the situation of 200mg/l, reuses 20 times, and loading capacity does not still have obvious reduction.
The working method of embodiment 2, embodiment 3 is with embodiment 1, and operating parameters sees Table 1.
Embodiment 4
Get chitosan 0.5g, be dissolved in the aqueous nitric acid of 30ml, 0.2M, add 3ml, the Ni of 2000mg/l
2SO
4The aqueous solution, treat chitosan dissolving after, add the citric acid mycelia of 10g through grinding and processing, mycelia particle diameter≤0.25mm coats with fluidized-bed, operating gas velocity 20m/s coats time 12h.Dropwise 5 ml ethylene glycol bis shrink glycidyl ethers, 20 ℃ of crosslinking temperatures, crosslinking time 12 hours.Filtration is arrived neutral with deionized water wash, add 200ml NaOH and make solidifying agent, solidify concentration 1% (w/w), solidify after 6 hours, filtration is arrived neutral with deionized water wash, the hydrochloric acid that adds 200ml 0.1M is cooked strippant, and to neutral, the NaOH that adds 1M 200ml cooks regenerator with deionized water wash for desorption time 6 hours, filtration, regenerated 10 minutes, filtration, is dried to neutral with deionized water wash, and the dried resin that obtains is the surface and coats the trace biological adsorption agent.Get 0.15g dried resin and 50ml Ni
2SO
4The aqueous solution joins in the Erlenmeyer flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Loading capacity be 89mg/g.Show and in the scope of pH=2～11 broads, to use by experimental result; At Ni
2+Concentration is under the situation of 400mg/l, can use 20 times, and loading capacity does not still have obvious reduction.
The working method of embodiment 5, embodiment 6, embodiment 7 is with embodiment 4, and operating parameters sees Table 2.
Comparative Examples 1
Get dried mould mycelia of 0.15g and 50ml Ni
2SO
4The aqueous solution joins in the Erlenmeyer flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Loading capacity be 20.1mg/g.Access times 3 times, loading capacity obviously reduces.
Comparative Examples 2
Get 0.15g pure chitosan and 50ml Ni
2SO
4The aqueous solution joins in the Erlenmeyer flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Loading capacity be 45mg/g.PH can not be lower than 4.0 during use.
Table 1
Table 2
Claims (10)
1, a kind of mycelium surface coated biologic adsorbent, it is characterized in that: make core material by mycelium, one deck coating layer is arranged outside mycelium, mycelium is citric acid fungus, yeast, Penicillium notatum or fungi, coating layer material is crosslinked dextran, chitosan or chitosan derivatives, mycelium particle diameter≤3mm, coating layer material and mycelial amount ratio are 1～0.01g/g.
2, biological adsorption agent according to claim 1 is characterized in that: chitosan derivatives is cm-chitosan, N-cm-chitosan, grafting cm-chitosan, chitosan phendioxin 5-hat-5 ethers or chitosan phendioxin 8-hat-6 ethers.
3, the preparation method of biological adsorption agent according to claim 1, coating layer material is dissolved in the acid, sour and mycelial amount ratio is 3～20m1/g, mix with mycelium then through the particle diameter≤3mm of fragmentation, adding linking agent again mixed crosslinked 0.5～24 hour down at 10～80 ℃, the add-on of linking agent and mycelial amount ratio are 0.01～10ml/g, crosslinked after filtration washing, add solidifying agent alkali lye, the concentration of solidifying agent alkali lye is 0.5%～20%, the add-on of solidifying agent alkali lye and mycelial amount ratio are 10～50ml/g, and drying obtains surface coated biologic adsorbent again.
4, the preparation method of biological adsorption agent according to claim 3, it is characterized in that: be dissolved in the acid back at coating layer material and add the trace solion, trace solion concentration is 20～10000mg/L, trace solion and coating layer material amount ratio are 5～50ml/g, add strippant behind crosslinked, filtration washing, strippant concentration is 0.01～0.5mol/L; Strippant and mycelial amount ratio are 10～50ml/g; Filtration washing adds regenerator once more, and regenerator concentration is 0.05～1mol/L, and regenerator and mycelial amount ratio are 10～50ml/g; Drying obtains the surface and coats the trace biological adsorption agent.
5, according to the preparation method of claim 3 or 4 described biological adsorption agents, it is characterized in that: acid is acetate, oxalic acid, hydrochloric acid, sulfuric acid or nitric acid.
6, the preparation method of biological adsorption agent according to claim 3 is characterized in that: linking agent is ethylene glycol bis shrink glycidyl ethers, glutaraldehyde, formaldehyde, epoxy chloropropane, vulcabond or ethylene glycol bis glycidyl ether.
7, the preparation method of biological adsorption agent according to claim 3 is characterized in that: solidifying agent alkali lye is sodium hydroxide, ammoniacal liquor, tripoly phosphate sodium STPP or sodium bicarbonate.
8, the preparation method of biological adsorption agent according to claim 4 is characterized in that: the trace solion is nickel, chromium, copper, silver, zinc or cadmium salt soln.
9, the preparation method of biological adsorption agent according to claim 4 is characterized in that: strippant is hydrochloric acid, nitric acid, sulfuric acid, acetate or sequestrant, and sequestrant is iminodiethanoic acid, ether azoles or disodium edta.
10, the preparation method of biological adsorption agent according to claim 4 is characterized in that: regenerator is sodium hydroxide, sodium bicarbonate, yellow soda ash or ammoniacal liquor.
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