CN104386831B - A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater - Google Patents
A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater Download PDFInfo
- Publication number
- CN104386831B CN104386831B CN201410723127.6A CN201410723127A CN104386831B CN 104386831 B CN104386831 B CN 104386831B CN 201410723127 A CN201410723127 A CN 201410723127A CN 104386831 B CN104386831 B CN 104386831B
- Authority
- CN
- China
- Prior art keywords
- hexavalent chromium
- substratum
- chromium wastewater
- additive
- waste water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- 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
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
-
- 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
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- Biomedical Technology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Virology (AREA)
- Medicinal Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses a kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater, object is to solve hexavalent chromium wastewater serious environment pollution, affects the problem of HUMAN HEALTH.Comprise and prepare immobilization microorganism particles, process waste water.Wherein, in step 1, microbial inoculum is dissolved in sodium alginate soln, and add additive, form mixing solutions, then mixing solutions is added in calcium chloride solution, obtain embedded particles, by the static solidification of embedded particles, and after brine, being fixed microbe granular.The present invention, by additive, the selection of substratum and cooperation, effectively can improve the treatment effect to hexavalent chromium wastewater, significantly promote processing efficiency, meet the requirement of industrial treatment hexavalent chromium wastewater.Process hexavalent chromium wastewater of the present invention, has the advantages such as cost is low, equipment investment is little, easy to operate, has wide market outlook and using value, is worth large-scale promotion, application.
Description
Technical field
The present invention relates to sewage treatment area, especially containing the process of hexavalent chromium wastewater, be specially a kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater.
Background technology
Chromium is as a kind of important metallic element, and it is one of industrial most widely used metal.Due to the extensive application of chromium, cause a large amount of generations of chromate waste water, the industries such as plating, metallurgy, process hides, paint, pigment, printing and dyeing, pharmacy and manufacture special steel thereof are all the main sources containing Cr (VI) waste water.In industrial chromium-containing waste water, chromium mainly exists with sexavalence form (Cr (VI)).The toxicity of chromium is relevant with the valence state of its existence, and sexavalent chrome is higher than trivalent chromium toxicity 100 times; Because chromium has " three cause " effect, and be easy to permeates cell membranes, cause various acute and chronic disease, therefore, the process problem strategic point of Cr (VI) waste water is to be solved.
At present, the treatment process of hexavalent chromium wastewater mainly contains Physical, chemical method and biological process.Wherein, biological process has the advantages such as investment is little, working cost is low, non-secondary pollution, obtains and develops faster.The application provides a kind of method adopting treatment based on immobilized microorganisms to contain hexavalent chromium wastewater.
Summary of the invention
Goal of the invention of the present invention is: for hexavalent chromium wastewater serious environment pollution, affects the problem of HUMAN HEALTH, provides a kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater.The present invention, by additive, the selection of substratum and cooperation, effectively can improve the treatment effect to hexavalent chromium wastewater, significantly promote processing efficiency, meet the requirement of industrial treatment hexavalent chromium wastewater.Process hexavalent chromium wastewater of the present invention, has the advantages such as cost is low, efficiency is high, equipment investment is little, easy to operate, has wide market outlook and using value, is worth large-scale promotion, application.
To achieve these goals, the present invention adopts following technical scheme:
A method for treatment based on immobilized microorganisms hexavalent chromium wastewater, comprises the steps:
(1) immobilization microorganism particles is prepared
The microbial inoculum of process hexavalent chromium wastewater is dissolved in sodium alginate soln, add additive wherein again, obtain mixing solutions, after mixing solutions mixing, then mixing solutions to be added mass concentration be in the calcium chloride solution of 0.5%-5%, obtains embedded particles, after static for embedded particles solidification 0.5-6h, embedded particles is taken out, and after cleaning with physiological saline, obtains immobilization microorganism particles;
(2) waste water is processed
Immobilization microorganism particles is added in chromyl waste water, concussion 0.5-120h, then the immobilization microorganism particles after process is separated, obtain the waste water after purification;
In described step 1, the mass concentration of sodium alginate of process hexavalent chromium wastewater is 0.1%-5%, and the mass ratio of sodium alginate and additive is 3:0.5-8, and described additive is one or more in carbon nanotube, gac, stalk.
In described step 1, calcium chloride solution mass concentration is 1%.
In described step 2, add the quality of immobilization microorganism particles in sodium alginate, 1g sodium alginate process Cr
6+quality be 2-10mg.
In described step 2, add the quality of immobilization microorganism particles in sodium alginate, 1g sodium alginate process Cr
6+quality be 4mg.
In described step 2, get chromyl waste water, be designated as waste water one, in waste water one, add immobilization microorganism particles and LB substratum, concussion 0.5-120h, then the immobilization microorganism particles after process is separated, obtain the waste water after purification;
The add-on of described LB substratum and the volume ratio of waste water one are 15-100:100;
Described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: agar: distilled water=2-8:7-13:7-13:12-18:1000, and the pH value of described LB substratum is 7.0-7.5;
Or described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: distilled water=5:10:10:1000, the pH value of described LB substratum is 7.2-7.4.
Described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: agar: distilled water=5:10:10:15:1000, and the pH value of described LB substratum is 7.2-7.4.
For hexavalent chromium wastewater serious environment pollution, affect the problem of HUMAN HEALTH, the invention provides a kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater.The method comprises prepares immobilization microorganism particles, process waste water two steps.Wherein, in step 1, microbial inoculum is dissolved in sodium alginate soln, and add additive, form mixing solutions, then mixing solutions is added in calcium chloride solution, obtain embedded particles, by the static solidification of embedded particles, and after brine, being fixed microbe granular.The present invention adopts immobilized microorganism technique, and free microorganism can be positioned the area of space limited by it, makes it keep active, and can Reusability.Adopt the method, that the concentration of process Cr (VI) waste water microbial inoculum is easy to control, resistance to murder by poisoning ability is comparatively strong, bacterial classification runs off is less, shock resistance good, efficiency is high, there is certain repetitive operation, and operational outfit is simple, there is larger advantage, for production practice, there is important practical value.Wherein, additive and substratum have material impact for the effect processing hexavalent chromium wastewater, and known by experiment of the present invention, three kinds of additives all can improve the removal effect of immobilization system to Cr (VI), lifting reaches about 30%, but between each additive, difference is not remarkable.Meanwhile, substratum of the present invention also has considerable influence for the treatment effect improving hexavalent chromium wastewater, and the substratum of interpolation 40% can significantly improve the removal ability to Cr (VI), and maximum material removal rate reaches more than 98%.By subsequent experimental, can know: additive, substratum can be good at improving in the present invention and solidify the removal effect of microorganism to Cr (VI) waste water, and the present invention is expected to be used widely in pollution of chromium waste water.
On this basis, be cured by immobilization microorganism particles in the embodiment of the present invention, result shows: bacterium is useless in during for 1:9, the subtilis (Bacillussubtilis) filtered out in Cr (VI) solution of 10mg/L clearance up to 100%, 30mg/L in also can reach more than 90%.
At microbial method processing waste water containing chrome (Geng Zhenxiang, Sun Ying etc., chemical engineer, 2003,95 (2): 6-8) in, report with useless Cr (VI) solution than the 100mg/L of (bacteria liquid sum waste liquid volume ratio) 1:1 of intestinal bacteria process bacterium, clearance reaches 99%; Microbial method process is containing the research (Huo Jianguo etc. of chromium (VI) waste water, chemical industry environmental protection, 2005,25 (1): 1-4.) in, report and process bacterium with sulphate reducing bacteria (SRB) and give up than Cr (VI) solution of the 150mg/L of 1:1, clearance reaches 99%.By contrast, this research adopts subtilis process bacterium to give up than Cr (VI) solution of 1:9, and its clearance is appreciable.
The present invention sets about from additive, substratum two aspect, prepares immobilization microorganism particles, and it is a kind of low cost, high efficiency treatment based on immobilized microorganisms system.The present invention has investigated the additives such as CNTs (carbon nanotube), gac and stalk, and nutrition source, and during with microbial inoculum effect, to the treatment effect of hexavalent chromium wastewater, experimental result shows: it has good treatment effect.In summary, additive and substratum all well can improve the treatment effect of immobilized microorganism technique to hexavalent chromium wastewater.Process hexavalent chromium wastewater of the present invention, has the advantages such as cost is low, efficiency is high, equipment investment is little, easy to operate, has wide market outlook and using value, is worth large-scale promotion, application.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the tolerance effect figure of subtilis (Bacillussubtilis) to Cr (VI).
Fig. 2 is the removal effect figure of subtilis (Bacillussubtilis) to Cr (VI).
Fig. 3 is the removal effect figure of CNTs additive to Cr (VI).
Fig. 4 is the removal effect figure of gac additive to Cr (VI).
Fig. 5 is the removal effect figure of stalk additive to Cr (VI).
Fig. 6 is the removal effect figure of substratum concentration to treatment based on immobilized microorganisms Cr (VI).
Fig. 7 is the removal effect figure of immobilized microorganism to different concns Cr (VI) solution.
Fig. 8 is the clearance figure of immobilization mixed bacterium to 40mg/LCr (VI).
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
(1) measure
The preparation of 1.1 main agents
DPC (phenylbenzene phosphinylidyne two hydrazine), analytical pure, Tianjin good fortune chemical reagent factory in morning; Potassium bichromate, analytical pure, Chengdu Ke Long chemical reagent factory.
DPC reagent: take 0.2gDPC medicine and be dissolved in the acetone of 50mL, then be settled to 100mL with pure water.Be stored in brown bottle, preserve at 4 DEG C.
1:1 phosphoric acid: by the proportioning preparation of phosphoric acid and pure water by volume 1:1.
1:1 sulfuric acid: by the proportioning preparation of the sulfuric acid of 98% and pure water by volume 1:1.
The hexavalent chromium solution of 5g/L: first potassium bichromate is toasted 2h at the temperature of 110 DEG C.Take 14.1435g potassium bichromate pure water constant volume again in 1000mL water.The hexavalent chromium solution of desired concn is become again by mother liquor.
1.2 key instrument
GH type water proof incubator, Tianjin Stettlen Instrument Ltd.; SW-CJ-1F Bechtop, safe and sound company of Su Jing group; GR60DA type ZEALWAY automatic pressure steam sterilization pan, Zealway (Xiamen) Instrument Inc.; THZ-98AB type constant temperature oscillator, Shanghai Yiheng Scientific Instruments Co., Ltd; SPECORD200PLUS type ultraviolet-visible pectrophotometer, Analytik Jena AG.
1.3 experimental technique
1.3.1Cr (VI) strength of solution measuring method
Adopt diphenyl carbazide spectrophotometry (GB7466-87).
(2) specific embodiment
Embodiment 1
Strains tested XJ-II: the dominant strain be isolated from Saline Ground in Xinjiang, is accredited as subtilis (Bacillussubtilis), optimum growth temp 37 DEG C.
The present embodiment removes the effect of hexavalent chromium in order to measure XJ-II, concrete operations are as follows.
Get slant strains XJ-II, be inoculated in 100mL liquid nutrient medium, in isothermal vibration incubator in 37 DEG C, cultivate 18h under 120r/min after seed liquor.Get OD
600the seed liquor of=0.8, the inoculum size with 10% is inoculated in Cr (VI) solution of different concns respectively.Take out certain quantity of fluid at set intervals in 60h, measure bacterial concentration OD
600, each experiment 3 repetitions, lower same, take substratum as contrast.Centrifuging and taking supernatant, measures Cr (VI) content residual in solution, take pure water as contrast.
Cr (VI) solution is processed with inoculum size inoculation subtilis (Bacillussubtilis) of 10%, investigate it to the tolerance effect of Cr (VI) and removal effect, experimental data is as shown in following table 1, table 2, and result as depicted in figs. 1 and 2.
Table 1 subtilis (Bacillussubtilis) is to the tolerance effect of Cr (VI)
Table 2 subtilis (Bacillussubtilis) is to the removal effect of Cr (VI)
As can be known from Fig. 1, tolerance curve does not have obvious lag phase, directly enters logarithmic phase.Control group (0mg/L) reaches maximum value at 24h; Under 10-50mg/L concentration, bacterial concentration reduces successively, and illustrate that Cr (VI) concentration is larger, thalline is suppressed stronger, and the tolerance of thalline is poorer, and growth velocity is slower; Under 10mg/L, 20mg/L and 40mg/L concentration, the same control group of Changing Pattern, reaches maximum value at 24h; Under 30mg/L concentration, reach maximum value at 36h; Under 50mg/L concentration, reach maximum value at 12h; The maximum value of bacterium has occurred that a priority moves the phenomenon moved forward again, when may be due to lower concentration, the growth of bacterium is suppressed, poor growth, move after maximum value, along with the continuation of Cr (VI) concentration increases, cannot continued growth after bacteria growing to certain phase, therefore, maximum value is reached soon.
As can be seen from Figure 2, under 10-50mg/L, subtilis (Bacillussubtilis) all shows has removal effect to Cr (VI).Under the concentration of 10mg/L, during 24h, reach maximum material removal rate; Under the concentration of 20-50mg/L, all reach maximum material removal rate when 36h; Illustrate that Cr (VI) strength of solution is larger, the growth of bacterium is more suppressed, and show and just extend the removal time of Cr (VI), and maximum material removal rate reduces with the increase of Cr (VI) concentration.The clearance that the clearance of 10mg/L can reach 100%, 30mg/L also can reach more than 90%.The present embodiment adopts subtilis process bacterium to give up than Cr (VI) solution of 1:9, and its clearance is appreciable.
Embodiment 2 additive is on the impact for the treatment of based on immobilized microorganisms Cr (VI)
2.1 experimental technique
Be the technical study of being fixed of additive with CNTs (carbon nanotube), gac and stalk respectively, process Cr (VI) solution.
Get 100mL and cultivate 14h, OD
600thalline (XJ-II) centrifuged deposit of=2.0, dissolving in 10mL final concentration is in the SA solution of 1.5%, add the single additive of 0.05g, 0.1g, 0.15g, 0.2g and 0.25g more respectively, instill in 1% calcium chloride solution after stirring, take out after immobilization 1h, physiological saline is cleaned, for subsequent use.
The immobilization microorganism particles containing additive of preparation is added in Cr (VI) solution of 100mL10mg/L, in 60h, measures Cr (VI) content residual in solution at set intervals.There is no the immobilization particle of additive for contrasting one, with the immobilization particle containing 0.25g additive for contrasting two, with immobilization microorganism particles for contrasting three.
2.2CNTs additive is to the removal effect of Cr (VI)
The immobilization microorganism particles that CNTs makes containing additive as additive is processed Cr (VI), Cr (VI) content residual in solution is measured at set intervals in 60h, experimental data is as shown in table 3, and result as shown in Figure 3.
Table 3CNTs additive is to the removal effect of Cr (VI)
In Fig. 3, control group one: immobilization particle; Control group two: containing the immobilization particle of 0.25gCNTs; Control group three: immobilization microorganism particles.
As shown in Figure 3, control group one is the removal effect of immobilization particle to Cr (VI), removes and takes the lead in slightly reducing after increase, tend to be steady afterwards, illustrate that immobilization material SA has certain removal effect to Cr (VI) solution.Owing to being physical material absorption, therefore within very short time, (6h) reaches adsorption rate climax, along with prolongation and the concussion of time, Cr (VI) solion being adsorbed on surface comes back in the aqueous solution, so Cr (VI) strength of solution rises slightly, clearance declines slightly, and 60h clearance is about 7%.Control group two is that the clearance short period of time rises fast, and 6h is tending towards maximum value, afterwards without considerable change containing the immobilization particle of 0.25gCNTs to the removal effect of Cr (VI).60h clearance is 13.06%.Control group three is the removal effect of immobilization microorganism particles to Cr (VI) solution, and the clearance same short period of time rises fast, slowly rises afterwards, finally tends to be steady, and 60h clearance is 24.66%.From three control groups, immobilization material, additive and thalline all have removal effect to Cr (VI), and clearance thalline is greater than additive is greater than immobilization material.
From experimental group, trend stably gradually after having the clearance of the immobilized experimental group of CNTs, thalline and SA to Cr (VI) all to present first fast to increase, the increase of CNTs amount is not remarkable on the impact of Cr (VI) solution removal rate, the clearance of five experimental group to Cr (VI) reaches the highest at 60h, is about 30%.From experimental group and three control groups of 0.25gCNTs, the removal effect of experimental group to Cr (VI) is greater than all control groups, illustrates that CNTs removes Cr (VI) to immobilized microorganism and has certain effect.
2.3 gac additives are to the removal effect of Cr (VI)
The immobilization microorganism particles that gac makes containing additive as additive is processed Cr (VI), Cr (VI) content residual in solution is measured at set intervals in 60h, experimental data is as shown in table 4, and result as shown in Figure 4.
Table 4 gac additive is to the removal effect of Cr (VI)
In Fig. 4, control group one: immobilization particle; Control group two: containing the immobilization particle of 0.25g gac; Control group three: immobilization microorganism particles.
As shown in Figure 4, control group one is the removal effect of immobilization particle to Cr (VI), analyzes same Fig. 3.Control group two is that the clearance short period of time rises fast, and 6h reaches maximum value, afterwards without considerable change containing the immobilization particle of 0.25g gac to the removal effect of Cr (VI).60h clearance is 13.48%.Control group three is the removal effect of immobilization microorganism particles to Cr (VI), analyzes same Fig. 3.
From experimental group, slowly increase after having the clearance of the immobilized experimental group of gac, thalline and SA to Cr (VI) solution all to present first increase fast, the trend tended to be steady afterwards.The increase of amounts of activated carbon is not remarkable on the impact of Cr (VI) solution removal rate, and five experimental group reach the highest to Cr (VI) solution removal rate at 48h, are about 35%.From experimental group and three control groups of 0.25g gac, the removal effect of experimental group to Cr (VI) is greater than all control groups, illustrates that gac is removed Cr (VI) to immobilized microorganism and had certain effect.
2.4 stalk additives are to the removal effect of Cr (VI)
The immobilization microorganism particles that stalk makes containing additive as additive is processed Cr (VI), Cr (VI) content residual in solution is measured at set intervals in 60h, experimental data is as shown in table 5, and result as shown in Figure 5.
Table 5 stalk additive is to the removal effect of Cr (VI)
In Fig. 5, control group one: immobilization particle; Control group two: containing the immobilization particle of 0.25g stalk; Control group three: immobilization microorganism particles.
As shown in Figure 5, control group one is the removal effect of immobilization particle to Cr (VI), analyzes same Fig. 3.Control group two is that the clearance short period of time rises fast, and 12h reaches maximum value, and afterwards without considerable change, 60h clearance is 11.44% containing the immobilization particle of 0.25g stalk to the removal effect of Cr (VI).Control group three is the removal effect of immobilization microorganism particles to Cr (VI), analyzes same Fig. 3.
From experimental group, trend stably gradually after having the clearance of the immobilized experimental group of stalk, thalline and SA to Cr (VI) solution all to present first fast to increase, the increase of stalk amount is not remarkable on the impact of Cr (VI) solution removal rate, five experimental group reach the highest to Cr (VI) solution removal rate at 36h, are about 30%.From experimental group and three control groups of 0.25g stalk, the removal effect of experimental group to Cr (VI) is greater than all control groups, illustrates that stalk is removed Cr (VI) to immobilized microorganism and had certain effect.
To sum up, in the present embodiment, adopt additive, existing immobilization microorganism particles can be made to form loose porous bulked state, increase its specific surface area, increase the contact area of thalline and substratum, strengthen the removal effect to Cr (VI).
CNTs, not remarkable to the removal efficiency difference of Cr (VI) between gac and stalk, trace it to its cause, it may be the pH value relying on solution because of three kinds of material removals to Cr (VI) all to a great extent, solution is remarkable to the removal effect of Cr (VI) in acid condition, the pH of solution rises to neutral to time alkaline, doubly, doubly, stalk clearance decline 2-3 doubly for gac clearance decline 2-3 for CNTs clearance decline 5-6; On the whole, in acid condition, the effect of CNTs is greater than gac and is greater than stalk; In this research after CNTs, gac and immobilized by stalk in neutrality in meta-alkalescence solution, about 3.5mg/g is to the adsorption rate of Cr (VI), namely in neutrality under meta-alkalescence condition, the removal difference of three kinds of additives to Cr (VI) is not obvious.Owing to not providing the nutrition source required for thalli growth, additive does not play its vital role, makes thalli growth, and therefore, providing of nutrition source will be the effective means playing additive effectiveness.Due to most of bacterial strain suitable growth temperature be in meta-alkalescence; and the physical strength of immobilization particle affects also quite large by pH; therefore find, to Cr (VI), there is high adsorption effect, can loose and porous structure be formed and the additive making the immobilization particle physical strength of formation higher is the task of top priority.
Embodiment 3
LB substratum composed as follows that the present embodiment adopts: yeast powder: 5g; Peptone: 10g; NaCl:10g; Agar: 15g; Distilled water: 1000mL.PH7.2-7.4 is regulated with 10%HCl/NaCl.During obtaining liq substratum, do not need to add agar.
In the present embodiment, the preparation method of immobilization microorganism particles is as follows: get 100mL and cultivate 14h, OD
600thalline (XJ-II) centrifuged deposit of=2.0, dissolving in 10mL final concentration is in the SA solution of 1.5%, then adds the CNTs of 0.25g, instills in 1% calcium chloride solution, take out after immobilization 1h after stirring, and physiological saline is cleaned, for subsequent use.
In Cr (VI) solution of 10mg/L, add 20% respectively, 40%, 60%, 80%, 100%LB substratum, with the above-mentioned solution of immobilization microorganism particles process 100mL, investigate substratum consumption to the impact of immobilization microorganism particles process Cr (VI).Wherein, in Cr (VI) solution of 10mg/L, add 20%LB substratum and refer to: containing 20mL substratum, 79.8mL pure water, 0.2mL sexavalent chrome mother liquor (the present embodiment adopts the hexavalent chromium solution of 5g/L to be mother liquor) in solution; And in Cr (VI) solution of 10mg/L, add 100%LB substratum to refer to: containing 99.8mL substratum, 0.2mL sexavalent chrome mother liquor (the present embodiment adopts the hexavalent chromium solution of 5g/L to be mother liquor) in solution, 0.2mL relative solution generally speaking, negligible, be therefore designated as 100%LB substratum.
substratum with 0% is contrast.experimental data is as shown in table 6 below, and result as shown in Figure 6.
Table 6 substratum concentration is to the removal effect for the treatment of based on immobilized microorganisms Cr (VI)
As shown in Figure 6, all curves all present first fast to rise and slowly rise, tend to be steady afterwards, finally slightly downward trend.The removal difference of all experimental group to Cr (VI) solution is not remarkable, may be because Cr (VI) strength of solution is lower, air neutralizes the bacterium added all has adsorption to Cr (VI) and the substratum added provides nutrition required for bacteria growing, causes the clearance of Cr (VI) higher.Finally be tending towards maximum material removal rate at 24h, the clearance of five groups of experimental group to Cr (VI) all reaches more than 90%.Control group be the substratum of 0% to the removal effect of Cr (VI), curve is comparatively steady, and clearance is lower, because do not have adding of substratum, cannot provide the nutrition source required for thalli growth, and thalli growth is slow, removes effect low; At 24h close to maximum material removal rate, afterwards without considerable change, clearance is only 24.74%.The removal effect of experimental group to Cr (VI) is far longer than control group, illustrates that the removal effect added improving Cr (VI) of substratum has great role.In order to provide to thalline more sufficient nutrient condition and reduce production cost, the substratum of follow-up selection 40% is studied as nutrition source.
On aforementioned base, more all add 40%LB substratum in Cr (VI) solution of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, with the above-mentioned solution of immobilization microorganism particles process 100mL.Cr (VI) content residual in solution is measured at set intervals in 60h.Take immobilization particle as contrast.Experimental data is in table 7, and result as shown in Figure 7.
Table 7 immobilized microorganism is to the removal effect of different concns Cr (VI) solution
As shown in Figure 7, all curves all present first increase after stable trend gradually.Contrast five experimental group, along with the increase of Cr (VI) concentration, the corresponding reduction of clearance; Illustrate that concentration is larger, the tolerance of bacterium is poorer, causes the clearance of Cr (VI) lower.All can more than 87% be reached to the clearance of the Cr (VI) of 10-30mg/L; Also can more than 60% be reached to the clearance of the Cr (VI) of 40mg/L, 50mg/L.Under the same terms, done the control experiment of different concns respectively, four control group data present the trend identical with experimental group, but clearance is more weak, illustrate that the contribution of microorganism in system in air is lower.After adding subtilis (Bacillussubtilis), clearance obviously increases.Relatively subtilis (Bacillussubtilis) finds the clearance of Cr (VI) separately, during the lower concentrations such as 10-30mg/L, the clearance of this experimental group and the clearance of independent bacterium are more or less the same, but during the high densitys such as 40-50mg/L, the clearance of this experimental group is higher than the clearance of independent bacterium, may be because the bacterium in air and the subtilis (Bacillussubtilis) added have made contribution to the removal of Cr (VI) jointly.
The present embodiment increases by adding a certain amount of substratum the effect that immobilized microorganism removes Cr (VI), and it can provide the environment of milder for microorganism, extends its life cycle, strengthens its removal effect to Cr (VI).Therefore, the process of interpolation to hexavalent chromium wastewater of the application's nutrition source has indispensable meaning.
Embodiment 4
Ua bacterial strain: pile the dominant strain be isolated from Ruoergai uranium ore, atrophy genus bacillus (Bacillusatrophaeus), optimum growth temp 35 DEG C, optimum growh pH6.0-9.0, the alkaline-resisting bacterium of middle temperature.
HB bacterial strain: the reference culture bought from Chinese Culture Collection, Bacillus subtilis endophyticus (Bacillussubtilisvar.), optimum growth temp 37 DEG C.
XJ-II (being designated as II): the dominant strain be isolated from Saline Ground in Xinjiang, is accredited as subtilis (Bacillussubtilis), optimum growth temp 37 DEG C.
Be one group with the mixing thalline of Ua bacterial strain and HB bacterial strain, be designated as UA+HB; Be one group with the mixing thalline of II bacterial strain and HB bacterial strain, be designated as II+HB.
Get 100mL and cultivate 36h, OD
600the mixing thalline centrifuged deposit of=3.5, dissolving in 10mL final concentration is in the SA solution of 1.5%, instills in 1% calcium chloride solution, take out after immobilization 1h after stirring, and cleans with physiological saline, being fixed microbe granular, for subsequent use.
40%LB substratum is all added, with the above-mentioned solution of immobilization microorganism particles process 100mL of preparation in Cr (VI) solution of 40mg/L.Cr (VI) content residual in solution is measured at set intervals in 96h.Take immobilization particle as contrast.The present embodiment investigates mixed bacterium to the removal effect of Cr (VI), and result as shown in Figure 8.
As shown in Figure 8, the combination of Ua+HB and II+HB all shows has removal effect to Cr (VI).Ua+HB combination is tending towards maximum value to the Cr (VI) of 40mg/L at 60h clearance, is about 98%; The Cr (VI) of combination to 40mg/L of II+HB is tending towards maximum value at 60h clearance, is about 85%; Two combinations are all more than or equal to the clearance of single thalline to 40mg/L.
Owing to being still scattered in the waste water after process after free thalline process waste water, its separating difficulty is large, and post-processed not easily; And method of the present invention has the advantages such as simple to operate, post-processed is easy, have broad application prospects.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (3)
1. a method for treatment based on immobilized microorganisms hexavalent chromium wastewater, is characterized in that, comprises the steps:
(1) immobilization microorganism particles is prepared
The microbial inoculum of process hexavalent chromium wastewater is dissolved in sodium alginate soln, add additive wherein again, obtain mixing solutions, after mixing solutions mixing, then mixing solutions to be added mass concentration be in the calcium chloride solution of 0.5%-5%, obtains embedded particles, after static for embedded particles solidification 0.5-6h, embedded particles is taken out, and after cleaning with physiological saline, obtains immobilization microorganism particles;
(2) waste water is processed
Get chromyl waste water, be designated as waste water one, in waste water one, add immobilization microorganism particles and LB substratum, concussion 0.5-120h, then the immobilization microorganism particles after process is separated, obtain the waste water after purification;
In described step 1, the mass concentration of sodium alginate of process hexavalent chromium wastewater is 0.1%-5%, and the mass ratio of sodium alginate and additive is 3:0.5-8, and described additive is one or more in carbon nanotube, stalk;
The add-on of described LB substratum and the volume ratio of waste water one are 15-100:100;
Described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: agar: distilled water=2-8:7-13:7-13:12-18:1000, and the pH value of described LB substratum is 7.0-7.5;
Or described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: distilled water=5:10:10:1000, the pH value of described LB substratum is 7.2-7.4.
2. the method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater according to claim 1, it is characterized in that, in described step 1, calcium chloride solution mass concentration is 1%.
3. the method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater according to any one of claim 1-2, it is characterized in that, described LB substratum is made up of the component of following mass ratio: yeast powder: peptone: NaCl: agar: distilled water=5:10:10:15:1000, and the pH value of described LB substratum is 7.2-7.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410723127.6A CN104386831B (en) | 2014-12-03 | 2014-12-03 | A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410723127.6A CN104386831B (en) | 2014-12-03 | 2014-12-03 | A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104386831A CN104386831A (en) | 2015-03-04 |
| CN104386831B true CN104386831B (en) | 2016-03-30 |
Family
ID=52604812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410723127.6A Expired - Fee Related CN104386831B (en) | 2014-12-03 | 2014-12-03 | A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104386831B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891676A (en) * | 2015-06-08 | 2015-09-09 | 黑龙江省科学院高技术研究院 | Method for treating chromium-containing heavy metal wastewater by immobilized fungal spore process |
| CN104944596A (en) * | 2015-06-08 | 2015-09-30 | 黑龙江省科学院高技术研究院 | Method for treating hexavalent chromium wastewater by aspergillus niger spore |
| CN105647901B (en) * | 2016-02-18 | 2019-04-05 | 清华大学 | Process for immobilizing enzyme/microbe is prepared using the modified calcium alginate of graphene oxide |
| CN107185492A (en) * | 2017-06-27 | 2017-09-22 | 江苏长龙国际贸易有限公司 | A kind of method of adsorption treatment low-concentration chromate waste water |
| CN107399832A (en) * | 2017-08-08 | 2017-11-28 | 王婧宁 | A kind of cleanser of efficient process heavy metals in industrial wastewater |
| CN107475238B (en) * | 2017-09-04 | 2019-12-24 | 华中农业大学 | Lotus seed pot immobilized microorganism and preparation method and application thereof |
| CN108018229A (en) * | 2017-11-09 | 2018-05-11 | 中南大学 | A kind of hexavalent chrome reduction immobilized microbial inoculum and preparation method |
| CN108975494B (en) * | 2018-09-04 | 2021-03-19 | 燕山大学 | Method for treating black smelly water by using graphene modified straw material |
| CN109912044A (en) * | 2019-03-19 | 2019-06-21 | 中国地质大学（北京） | A kind of Waste water treatment medicament and its application method |
| CN110127859A (en) * | 2019-05-17 | 2019-08-16 | 西南科技大学 | A kind of chromium-containing solution processing method |
| CN110104796A (en) * | 2019-05-28 | 2019-08-09 | 陈方鑫 | A kind of wastewater treatment integration medicament and its application method |
| CN110241111B (en) * | 2019-06-17 | 2023-06-09 | 中南大学 | Method for enhancing bacterial chromium reduction capacity by modified activated carbon immobilized cells |
| CN113171753B (en) * | 2021-04-27 | 2022-01-28 | 西南科技大学 | Preparation of sodium alginate-zirconium phosphate composite beads and adsorption application of sodium alginate-zirconium phosphate composite beads in nuclear waste liquid |
| CN114958817B (en) * | 2022-06-24 | 2024-04-26 | 江苏大学 | Dual-core-shell loaded microbial material and preparation method and application thereof |
| CN115286119B (en) * | 2022-07-20 | 2023-09-12 | 西南科技大学 | Microorganism strengthening medicament for removing hexavalent chromium by taking minerals/biomass as carrier and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054563A (en) * | 2006-04-12 | 2007-10-17 | 中国科学院生态环境研究中心 | Fixation bacterium organism adsorbent for silver and preparation method thereof |
| CN101225379A (en) * | 2008-01-25 | 2008-07-23 | 东北农业大学 | Non-active immobilized yeast filler as well as preparation method thereof and method for treating heavy metal wastewater thereby |
| JP4503390B2 (en) * | 2004-08-03 | 2010-07-14 | メタウォーター株式会社 | Hazardous substance detection device and detection method |
| CN101818140A (en) * | 2010-04-28 | 2010-09-01 | 湖南大学 | Immobilization pseudomonas aeruginosa as well as preparation method and application thereof |
| CN103160492A (en) * | 2013-04-10 | 2013-06-19 | 哈尔滨理工大学 | Preparation method of immobilized bacillus subtilis and method for treating wastewater by using immobilized bacillus subtilis |
| CN104248945A (en) * | 2014-09-17 | 2014-12-31 | 华中科技大学 | Heavy metal adsorbent and preparation method and application thereof |
-
2014
- 2014-12-03 CN CN201410723127.6A patent/CN104386831B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4503390B2 (en) * | 2004-08-03 | 2010-07-14 | メタウォーター株式会社 | Hazardous substance detection device and detection method |
| CN101054563A (en) * | 2006-04-12 | 2007-10-17 | 中国科学院生态环境研究中心 | Fixation bacterium organism adsorbent for silver and preparation method thereof |
| CN101225379A (en) * | 2008-01-25 | 2008-07-23 | 东北农业大学 | Non-active immobilized yeast filler as well as preparation method thereof and method for treating heavy metal wastewater thereby |
| CN101818140A (en) * | 2010-04-28 | 2010-09-01 | 湖南大学 | Immobilization pseudomonas aeruginosa as well as preparation method and application thereof |
| CN103160492A (en) * | 2013-04-10 | 2013-06-19 | 哈尔滨理工大学 | Preparation method of immobilized bacillus subtilis and method for treating wastewater by using immobilized bacillus subtilis |
| CN104248945A (en) * | 2014-09-17 | 2014-12-31 | 华中科技大学 | Heavy metal adsorbent and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| "Batch and continuous flow studies of adsorptive removal of Cr(VI) by adapted";Jastin Samuel etal.;《Bioresource Technology》;20130131;第128卷;2. Methods，3. Results * |
| "Cr(VI) reduction by Pseudomonas aeruginosa immobilized in a polyvinyl";Ya Pang etal;《Bioresource Technology》;20111122;第102卷;2. Methods * |
| "Carbon nanotubes promote Cr(VI) reduction by alginate-immobilized";Fang-Fang Yan etal.;《Biochemical Engineering Journal》;20130815;第77卷;2.2. Preparation of Ca-alginate/CNT/cell beads，2.3. Cr(VI) reduction experiments * |
| "利用游离和固定化铬（Ⅵ）还原菌除铬的研究";杨锦霞;《中国优秀硕士学位论文全文数据库工程科技I辑》;20111231(第S1期);第2.1.2实验培养基及组分，2.2.1铬还原菌的筛选，2.2.7固定化菌株Q5-1还原铬（Ⅵ）的效果，3.7固定化菌株Q5-1还原铬（Ⅵ）的效果 * |
| "吸附融合菌的固定化及对铬吸附特性研究";李森等;《环境工程学报》;20100831;第4卷(第8期);1.2实验方法 * |
| "生物吸附剂处理含Cr（Ⅵ）废水的基础研究";王彩冬;《中国优秀硕士学位论文全文数据库工程科技I辑》;20081231(第9期);3.1.2海藻酸钙生物吸附剂的制备，3.2海藻酸钙生物吸附剂的影响因素研究 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104386831A (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104386831B (en) | A kind of method for the treatment of based on immobilized microorganisms hexavalent chromium wastewater | |
| Öztürk et al. | Biosorption of nickel (II) and copper (II) ions from aqueous solution by Streptomyces coelicolor A3 (2) | |
| Cui et al. | Bioremediation of heavy metal pollution utilizing composite microbial agent of Mucor circinelloides, Actinomucor sp. and Mortierella sp. | |
| Sun et al. | Preparation of a new-style composite containing a key bioflocculant produced by Pseudomonas aeruginosa ZJU1 and its flocculating effect on harmful algal blooms | |
| CN1900271B (en) | Ocean salt monad and its using method in biological flocculation and heavy metal adsorption | |
| Sağ et al. | A comparative study for the simultaneous biosorption of Cr (VI) and Fe (III) on C. vulgaris and R. arrhizus: application of the competitive adsorption models | |
| CN103834589B (en) | One Achromobacter xylosoxidans and application thereof | |
| CN104673715B (en) | There is fixed effect to cadmium and enterobacteria and its application of plant growth can be promoted | |
| CN103923867B (en) | Mixed bacterial microbial preparation and in process containing the application in nitric nitrogen waste water | |
| Zhou et al. | Effects of suspended titanium dioxide nanoparticles on cake layer formation in submerged membrane bioreactor | |
| CN107400650A (en) | One kind deformation pseudomonad and its application | |
| CN113072192B (en) | System and method for removing perfluorinated compounds in water by reinforced constructed wetland | |
| Nasseri et al. | Chromium removal from tanning effluent using biomass of Aspergillus oryzae | |
| CN106244471B (en) | Heavy metal mercury-resistant fungus strain and application thereof | |
| CN105944684A (en) | Preparation method and application of oxidized graphene and magnetic chitosan compound | |
| CN111014280A (en) | Method for repairing cadmium-polluted soil by using bacteria-montmorillonite compound | |
| CN110846246A (en) | Preliminary screening method for bacteria with ammonia nitrogen degradation function | |
| Morris et al. | Use of crustacean shells for uptake and removal of metal ions in solution | |
| CN101816920B (en) | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof | |
| CN108178337A (en) | A kind of activation accelerating agent for improving daily chemical wastewater microbiological treatment effect | |
| CN105400718A (en) | Nitrate dependent ferrous oxidization strain and application thereof | |
| CN107096507A (en) | A kind of preparation method and applications for the microbial adsorbent for handling heavy metals in industrial wastewater ion | |
| CN104513801B (en) | Radioresistance acinetobacter calcoaceticus（Acinetobacter radioresistens）Applications of the ZX2 in sulphate reducing | |
| CN105645599A (en) | Biological treatment method for reverse osmosis strong brine | |
| CN110357266A (en) | Utilize the method for heavy metal ion in sargassum thunbergii removal polluted-water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160330 Termination date: 20171203 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |