CN103951032B - A kind of sulfate reduction bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier - Google Patents
A kind of sulfate reduction bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier Download PDFInfo
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Abstract
Based on a sulfate reduction bacteria immobilization star biological active filling material preparations and applicatio for mesh carrier, belong to water treatment field.Star biological active filling material is by embedding body and carrier two portions form: carrier is with polyethylene, polypropylene etc. for main raw, and adds the netted star carrier of the water wetted materials such as polyvinyl alcohol through hot melt or sheet material hot pressing; The reticulated structure of carrier, can make embedding body run through mesh and carrier forms rivet clasp structure and increases filler resistance to overturning; Embedding liquid is mixed by sulphate reducing bacteria concentrated solution and polyvinyl alcohol solution and forms; Embedding liquid is spread evenly across on mesh carrier, forms embedding body after boric acid secondary crosslinking is fixing, and is incorporated into mesh carrier and obtains sulphate reducing bacteria biological active filling material.Biological active filling material prepared by the present invention, not only can effectively solve the problems such as sulphate reducing bacteria adhesive ability is poor, film-forming properties is poor, can also improve reactor for treatment ability, shortens start time.
Description
Technical field
The invention belongs to water treatment field, particularly a kind of sulfate reduction bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier.
Background technology
Utilizing sulphate reducing bacteria (Sulfate-ReducingBacteria, SRB) carry out in the treating processes of sulfate wastewater, the quantity of functional microorganism (mainly referring to sulphate reducing bacteria), metabolic activity and ecological factor directly affect the operation treatment efficiency of reactor.Due in the anaerobic treatment of sulfate wastewater, there is abundant carbon source (in waste water original or be process and the COD that adds) and suitable anaerobic condition, similar microorganism is assembled many site conditions, so how to keep the population superiority of SRB, suitable ecological factor and substrate competition advantage to be the research emphasis of srb assay process sulfate wastewater.At present, the main process of SRB process sulfate wastewater is utilized to have individual event anaerobic technique, individual event stripping process, diphasic anaerobic technique and bio membrane process.Traditional sulfate wastewater treatment technique also exists that the reactor start-up time is long, processing power is limited, SRB tack and film-forming properties poor, be difficult to form dominant microflora and there is the defects such as substrate competition with other anerobes, make it in actual applications there is limitation.In order to the deficiencies such as the adhesive ability improving SRB is poor, film-forming properties is poor and the shortcoming that the reactor start-up time is grown, many scholars start and utilize immobilized microorganism technology fix the experimental study of sulphate reducing bacteria and achieve certain achievement in research.
Microorganism cells immobilization technology can increase substantially biomass and the cell concn of functional microorganism in unit for treating water at short notice, the start time of reactor is shortened, microorganism number of dropouts reduce, the adaptive faculty that former water potential of hydrogen, toxicity, salinity etc. change obviously is strengthened.Utilize microorganism cells immobilization technology can create the ecological dominance of stable microorganisms with specific functions, produce the substance metabolism process of expection, demonstrate huge application prospect in water treatment field.Common microbial cell immobilization method has absorption method, crosslinking and entrapping method.Wherein, conventional with entrapping method, the material being successfully used to microorganism cells embedding has polyvinyl alcohol, agar, K-carrageenin, gelatin, sodium alginate, polyacrylamide, urethane etc.Above-mentioned embedded material have mass-transfer performance good, not easily by biological decomposition, stable performance, physical strength is high, long service life, price are low, to advantages such as microorganism are nontoxic.
At present, traditional bacterium embedding method research concentrate on how by bacterium with embedded material stable bond together with, formed and embed body, such as microballoon, embedded block etc.Although working method is simple, limitation is comparatively large, cannot be desirable be applied in the middle of engineering reality.We improve through studying for many years, embedding body and carrier are combined on traditional embedding method, form overall biological active filling material.Embedding body and the combination of carrier, make biological active filling material have more performance, and it combines the advantage that simple microbial bacterial and embedded material have.
By the combination of embedding body and carrier, the active filler of preparing has huge application advantage and wide application space.The selective gist of filling-material structure form and immobilization technology directly determines effect and the work-ing life of biological active filling material.Compare through experimental study, we find that the biological active filling material prepared based on conventional filler structure formation and the embedding method effect in test application is difficult to accomplish the end in view, also exist biological active filling material resistance to overturning poor, embed body and easily come off and the problems such as water-soluble.For the problems referred to above, the sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier that a kind of resistance to overturning that we develop is good is with a wide range of applications.
Summary of the invention
The object of the invention is to develop a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier, the reticulated structure design of this biological active filling material carrier, embedding body is made to form overall rivet clasp structure by mesh and carrier, embedding body difficult drop-off, and embed physical efficiency on reticulated structure, form millimetre-sized membrane structure, make that good, the overall permeability of biological active filling material resistance to overturning that obtains is good, mass transfer effect is higher.Mesh carrier is designed to star, all the time fluffy state is between biological active filling material, there will not be filler blocking, current short circuit problem, and the embedding body on each fin can not be subject to extraneous friction, ensure that the biomass of sulphate reducing bacteria, biological active filling material processing efficiency be high, stable performance.
In order to achieve the above object, present invention employs following technical scheme.
A kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier, it is characterized in that: immobilization star biological active filling material is fixedly bonded together by the limit of multi-disc net slice shape structured material the star structure formed, the embedding body wherein forming the involved thalline of twine of net slice shape structured material mesh is embedded by mesh, thus forming overall rivet clasp structure, embedding body forms millimetre-sized membrane structure on netted slab organization.Net slice shape structured material is long is 0.5-3cm, and wide is 0.5-3cm.Netted biological active filling material carrier is based on polyethylene, polyvinyl chloride, polypropylene, ABS resin material, add the water wetted materials such as the polyvinyl alcohol (PVA) of 6wt%-9wt%, make netted slab organization by modes such as strand hot melt molding or sheet material hot pressing pore-formings, its mesh form can be circle, rhombus, square, rectangle.The string diameter 0.5-2mm of preferred mesh.
The preparation method of above-mentioned a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier, is characterized in that, comprise the following steps:
(1) with polyethylene, polyvinyl chloride, polypropylene, ABS resin material is main, add the water wetted materials such as 6wt%-9wt% polyvinyl alcohol (PVA), the reticulated structure carrier of sheet shape is made by modes such as strand hot melt or sheet material hot pressing pore-formings, long is 0.5-3cm, wide is 0.5-3cm, hot melt extruded is passed through on the limit of the reticulated structure carrier of some shapes, the mode such as bonding is fixedly bonded together, the angle of arbitrary two adjacent sheet shape carriers is identical, make multi-form stellate reticulum carrier, such as: three can be used, four, five, six mesh carriers, make angle and be respectively 120 °, 90 °, 72 °, the multi-form stellate reticulum carrier of 60 °,
(2) by sulphate reducing bacteria concentrated solution and polyvinyl alcohol solution mixing, and add calcium carbonate and be prepared into embedding liquid, polyvinyl alcohol mass concentration is 80-100g/L, and calcium carbonate mass concentration is 10-40g/L;
(3) according to polyvinyl alcohol-boric acid secondary crosslinking method, embedding liquid in step (2) is uniformly coated on the outside surface of star structure carrier, after putting into saturated boric acid solution 1-3h, regulate boric acid solution pH to 8-10, crosslinked 3-24h, taken out, clean remained on surface material, obtain sulfate reduction bacteria immobilization star biological active filling material.
In carrier, the addition of polyvinyl alcohol (PVA) can suitably adjust as required, and this is prior art, and the mass percentage of preferably polyethylene alcohol (PVA) is 5%-10%.
A kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of the present invention is used for water treatment.
The beneficial effect of the sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of the present invention is mainly reflected in:
1. cancellated design, makes embedding body form overall rivet clasp structure by mesh and carrier, embedding body difficult drop-off, makes the biological active filling material resistance to overturning that obtains good, is conducive to keeping higher sulfate reduction bacteria biomass;
2. mesh carrier is designed to star, and this structure ensure that the embedding body between biological active filling material fin can not be subject to extraneous friction, is conducive to keeping higher sulfate reduction bacteria biomass, biological active filling material processing efficiency is high, stable performance;
3. experimental study shows, be the carrier immobilized biological active filling material poor stability obtained with conventional filler, in 2 days, embedded material almost all comes off, and the biological active filling material resistance to overturning obtained with mesh carrier immobilization is good, and the filler life-span is more than 3 years;
4. the sulphate reducing bacteria biological active filling material that immobilization is obtained, global density, between 0.95-1.10, can be made into floated or precipitation, and can make multi-form according to the demand of water treatment working condition;
5. mesh carrier is main raw by polyethylene, polyvinyl chloride, polypropylene, ABS resin, with the addition of the water wetted materials such as polyvinyl alcohol (PVA), improves the wetting ability of carrier, adds the intensity that carrier bonds with embedding body, improves overall stability;
6. biological active filling material due to the existence of mesh skeleton structure make embedding body can implementation structure thickness less while in turn enhance the adaptability that one-piece construction changes water treatment running environment, less thickness can improve the mass-transfer efficiency of substrate and the utilization ratio of embedding body, if make thickness like this with embedding body own material cannot realize good carrier performance in water technology processing unit;
7. embed the crosslinked fixing employing polyvinyl alcohol-boric acid secondary crosslinking method of body, biomass loss can be effectively reduced, be conducive to keeping the activity of sulphate reducing bacteria and the biomass of functional microorganism;
8. the sulphate reducing bacteria bag bacterium amount of immobilized biological activated filler is large, and SRB can set up flora advantage at short notice, and processing efficiency is high, good stability;
9. the surface of star biological active filling material be all embedded body cover, in addition embed body structure thinner, be conducive to sulphate reducing bacteria contact substrate, avoid the waste of material simultaneously, effectively raise the utilization ratio of carrier filler.
Accompanying drawing explanation
Fig. 1 is star sulphate reducing bacteria biological active filling material fin schematic diagram;
Fig. 2 is I-I diagrammatic cross-section of Fig. 1;
Fig. 3 is II-II diagrammatic cross-section of Fig. 1;
Fig. 4,5,6,7 is star sulphate reducing bacteria biological active filling material schematic diagram.
1. twines in figure, 2. embed body
Embodiment
Below in conjunction with case study on implementation, the present invention is more specifically described, but embodiments of the present invention are not limited thereto.
Embodiment 1
1. the preparation of mesh carrier
With high molecular polymers such as polypropylene for main raw, add the polyvinyl alcohol (PVA) of 6wt%, system grows into 1.0cm, and wide is the sheet shape mesh carrier of 0.7cm.Mesh form is square, and the length of side is 2mm, and string diameter is 1.5mm.By the stellate reticulum carrier of six sheet above shape carriers by hot melt, bonding formation angle 60 degree.
2. the preparation of sulphate reducing bacteria concentrated solution
By the sulphate reducing bacteria bacteria suspension centrifugal concentrating after amplification cultivation, obtain 3.5 × 10
9the concentrated solution of the sulphate reducing bacteria of individual/mL.
3. embed the preparation of liquid
Weighing polyvinyl alcohol 5kg, adds 25L ultrapure water post-heating to 85 DEG C, dissolves 15min.The polyvinyl alcohol solution of dissolving taken out and reheats 5min after stirring, after stirring, being cooled to 31 ± 1 DEG C.25L polyvinyl alcohol solution and the 25L sulphate reducing bacteria concentrated solution mixing prepared, and add 1.3kg calcium carbonate, namely make 50L after stirring and embed liquid.
4. embed the combination of liquid and mesh carrier
Embedding liquid is uniformly coated on mesh carrier surface, guarantees that mesh carrier surface is all embedded liquid uniform fold.
5. the preparation of sulphate reducing bacteria biological active filling material
The mesh carrier smearing embedding liquid in step (4) is put into saturated boric acid solution, it is made to be in submerged condition, leave standstill 3h to be cross-linked, regulator solution pH to 9.0, standing 4h completes fixing, cleaning, obtain sulphate reducing bacteria biological active filling material, this biological active filling material proportion is between 1.05-1.10.
6. the application of sulphate reducing bacteria biological active filling material
To 0.5m
3synthetic glass column type reactor in add embedded star biological active filling material, filling ratio is 60%, and water temperature is 24 DEG C-26 DEG C, and HRT=12h, pH are 7.5-8.0, ORP≤-310mV, using Sodium.alpha.-hydroxypropionate as organic carbon source, SO
4 2-concentration is 1000 ± 10mg/L, ensures COD/SO
4 2->=2, biological active filling material is in precipitated form in the reactor, every day assaying reaction device sulfate reduction effect.Water outlet detected result shows, reactor runs to the 7th day, and the reduction effect of vitriol is stablized.SO in water outlet
4 2-concentration is 69-93mg/L, and clearance remains on more than 90%, and reactor runs 1 year continuously, sulfate reduction effect stability, and the percentage of head rice of biological active filling material reaches 92%.
Embodiment 2
1. the preparation of mesh carrier
With high molecular polymers such as polyethylene for main raw, add the polyvinyl alcohol (PVA) of 5wt%, system grows into 1.0cm, and wide is the sheet shape mesh carrier of 0.7cm.Mesh form is square, and the length of side is 2mm, and string diameter is 1.5mm.By the stellate reticulum carrier of six sheet above shape carriers by hot melt, bonding formation angle 60 degree.
2. the preparation of sulphate reducing bacteria concentrated solution
By the sulphate reducing bacteria bacteria suspension centrifugal concentrating after amplification cultivation, obtain 7.5 × 10
9the concentrated solution of the sulphate reducing bacteria of individual/mL.
3. embed the preparation of liquid
Weighing polyvinyl alcohol 5kg, adds 25L ultrapure water post-heating to 85 DEG C, dissolves 15min.The polyvinyl alcohol solution of dissolving taken out and reheats 5min after stirring, after stirring, being cooled to 31 ± 1 DEG C.25L polyvinyl alcohol solution and the 25L sulphate reducing bacteria concentrated solution mixing prepared, and add 1kg calcium carbonate, namely make 50L after stirring and embed liquid.
4. embed the combination of liquid and mesh carrier
Embedding liquid is uniformly coated on mesh carrier surface, guarantees that mesh carrier surface is all embedded liquid uniform fold.
5. the preparation of sulphate reducing bacteria biological active filling material
The mesh carrier smearing embedding liquid in step (4) is put into saturated boric acid solution, it is made to be in submerged condition, leave standstill 3h to be cross-linked, regulator solution pH to 9.0, standing 4h completes immobilization, cleaning, obtain sulphate reducing bacteria biological active filling material, this biological active filling material proportion is between 0.98-1.02.
6. the application of sulphate reducing bacteria biological active filling material
To 0.5m
3synthetic glass column type reactor in add embedded star biological active filling material, filling ratio is 60%, and water temperature is 24 DEG C-26 DEG C, and HRT=8h, pH are 7.5-8.0, ORP≤-310mV, using Sodium.alpha.-hydroxypropionate as organic carbon source, SO
4 2-concentration is about 2000 ± 15mg/L, ensures COD/SO
4 2->=2.Reactor increases the upflow velocity of water by effluent recycling mode, makes biological active filling material be in fluidized state in the reactor.Every day assaying reaction device vitriol removal effect.Water outlet detected result shows, reactor runs to the 8th day, and the reduction effect of vitriol is stablized.Water outlet SO
4 2-concentration is 148-197mg/L, and clearance remains on more than 90%.Reactor runs 1 year continuously, sulfate reduction effect stability, and the percentage of head rice of filler reaches 94%.
Above-mentioned example shows, the sulfate reduction bacteria immobilization star biological active filling material making processes based on mesh carrier is simple, and obtained biological active filling material resistance to overturning is good, embedding body difficult drop-off, bacterial concentration are higher.
Claims (5)
1. the sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier, it is characterized in that: immobilization star biological active filling material is fixedly bonded together by the limit of multi-disc net slice shape structured material the star structure formed, the twine wherein forming net slice shape structured material mesh is embedded by mesh by the embedding body of Containing Sulfate Reducing Bacteria, thus form overall rivet clasp structure, embedding body forms millimetre-sized membrane structure on netted slab organization, wherein netted biological active filling material carrier is with polyethylene, polyvinyl chloride, polypropylene, ABS resin material is main, add polyvinyl alcohol (PVA) water wetted material.
2. a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of claim 1, is characterized in that: net slice shape structured material is long is 0.5-3cm, and wide is 0.5-3cm.
3. a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of claim 1, it is characterized in that: netted biological active filling material carrier is based on polyethylene, polyvinyl chloride, polypropylene, ABS resin material, add polyvinyl alcohol (PVA) water wetted material, netted slab organization is made by strand hot melt molding or sheet material hot pressing pore-forming mode, its mesh form is the string diameter 0.5-2mm of circle, rhombus, rectangle, mesh.
4. prepare the method for a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier described in any one of claim 1-3, it is characterized in that, comprise the following steps:
(1) based on polyethylene, polyvinyl chloride, polypropylene, ABS resin macromolecular material, add polyvinyl alcohol (PVA) water wetted material, the reticulated structure carrier of sheet shape is made by strand hot melt or sheet material hot pressing pore-forming mode, long is 0.5-3cm, wide is 0.5-3cm, fixedly be bonded together by hot melt extruded, bonding way on the limit of the reticulated structure carrier of some shapes, the angle of arbitrary two adjacent sheet shape carriers is identical, makes multi-form stellate reticulum carrier;
(2) by sulphate reducing bacteria concentrated solution and polyvinyl alcohol solution mixing, and add calcium carbonate and be prepared into embedding liquid;
(3) according to polyvinyl alcohol-boric acid secondary crosslinking method, embedding liquid in step (2) is uniformly coated on the outside surface of star structure carrier, after putting into saturated boric acid solution 1-3h, regulate boric acid solution pH to 8-10, crosslinked 3-24h, taken out, clean remained on surface material, obtain sulfate reduction bacteria immobilization star biological active filling material.
5. the arbitrary described a kind of sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of claim 1-3 is used for water treatment.
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| CN103194437A (en) * | 2013-04-12 | 2013-07-10 | 北京工业大学 | Method for finishing bacterium fixation by utilizing polyvinyl alcohol-borate secondary crosslinking |
| CN103657399A (en) * | 2012-09-06 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of macromolecule activated carbon composite filler |
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| JP2548871B2 (en) * | 1992-09-18 | 1996-10-30 | 日本碍子株式会社 | Method for producing immobilized carrier |
| JP2001347286A (en) * | 2000-06-06 | 2001-12-18 | Rengo Co Ltd | Porous hollow article, microorganism immobilizing carrier using the same and method for manufacturing porous hollow article |
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| CN103657399A (en) * | 2012-09-06 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of macromolecule activated carbon composite filler |
| CN103194437A (en) * | 2013-04-12 | 2013-07-10 | 北京工业大学 | Method for finishing bacterium fixation by utilizing polyvinyl alcohol-borate secondary crosslinking |
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