CN103951032A - Preparation and application of sulfate reducing bacteria immobilized star-shaped bioactive filler based on reticulate carrier - Google Patents
Preparation and application of sulfate reducing bacteria immobilized star-shaped bioactive filler based on reticulate carrier Download PDFInfo
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Abstract
The invention discloses preparation and an application of a sulfate reducing bacteria immobilized star-shaped bioactive filler based on a reticulate carrier, and belongs to the technical field of water treatment. The star-shaped bioactive filler comprises two parts: an embedding body and the carrier; the carrier is a reticulate star-shaped carrier formed by taking polyethylene or polypropylene and the like as a main material, adding polyvinyl alcohol or other hydrophilic materials and carrying out hot melting or plate hot pressing; with a reticulate structure of the carrier, the embedding body can be allowed to penetrate through meshes to form a riveting fixing structure together with the carrier so as to increase the filler overall stability; an embedding liquid is formed by mixing a sulfate reducing bacteria concentrated solution and a polyvinyl alcohol solution; the reticulate carrier is evenly coated with the embedding liquid, and the embedding body is formed after boric acid secondary cross-linking immobilization of the embedding liquid and is combined with the reticulate carrier to obtain the sulfate reducing bacteria bioactive filler. The prepared bioactive filler not only can effectively solve the problems that sulfate reducing bacteria are poor in adhesion ability, poor in film-forming ability and the like, but also can improve the processing ability of a reactor and shorten the start-up time.
Description
Technical field
The invention belongs to water treatment field, particularly a kind of preparation of sulfate reduction bacteria immobilization star biological active filling material and application based on mesh carrier.
Background technology
Utilizing sulphate reducing bacteria (Sulfate-Reducing Bacteria, SRB) carry out in the treating processes of sulfate wastewater, quantity, metabolic activity and the ecological factor of functional microorganism (mainly referring to sulphate reducing bacteria) directly affect the operation treatment efficiency of reactor.Due in the anaerobic treatment of sulfate wastewater, exist abundant carbon source (the original or COD that adds for processing in waste water) and suitable anaerobic condition, the similar microorganism of many site conditions is assembled, and is the research emphasis that srb assay is processed sulfate wastewater so how to keep the population superiority of SRB, suitable ecological factor and substrate competition advantage.At present, the main treatment process that utilizes SRB to process sulfate wastewater has individual event anaerobic technique, individual event stripping process, diphasic anaerobic technique and bio membrane process.Traditional sulfate wastewater treatment technique 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 have the defects such as substrate competition with other anerobes, make it to have in actual applications limitation.In order to improve long shortcoming of the deficiencies such as the adhesive ability of SRB is poor, film-forming properties is poor and reactor start-up time, many scholars have started utilize the experimental study of the fixing sulphate reducing bacteria of microbial immobilized technology and obtained 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, makes shortening start time, the microorganism number of dropouts of reactor reduce, the adaptive faculty of the variations such as former water potential of hydrogen, toxicity, salinity is obviously 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, the most conventional with entrapping method, the material that has been 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, be difficult for, long service life high by biological decomposition, stable performance, physical strength, price low, to advantages such as microorganism are nontoxic.
At present, how the research of traditional bacterium embedding method concentrate on bacterium with embedded material stable bond together with, formation embedding body, such as microballoon, embedded block etc.Although working method is simple, limitation is larger, cannot be desirable be applied in the middle of engineering reality.We,, through research for many years, improve on traditional embedding method, and embedding body and carrier are combined, and form overall biological active filling material.The combination of embedding body and carrier, makes biological active filling material have more performance, and it combines simple microbial bacterial and embedded material has advantages of.
The active filler of preparing by the combination of embedding body and carrier has huge application advantage and wide application space.The selection application of filling-material structure form and immobilization technology has directly determined effect and the work-ing life of biological active filling material.Through experimental study comparison, 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, the problems such as exist that biological active filling material resistance to overturning is poor, embedding body easily comes off and water-soluble.For the problems referred to above, the good sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier of a kind of resistance to overturning that we develop 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, make embedding body form overall rivet clasp structure by mesh and carrier, embedding body difficult drop-off, and embedding physical efficiency forms millimetre-sized membrane structure on reticulated structure, make that good, the overall permeability of biological active filling material resistance to overturning that makes is good, mass transfer effect is higher.Mesh carrier is designed to star, between biological active filling material all the time in fluffy state, there will not be filler obstruction, current short circuit problem, and embedding body on each fin can not be subject to extraneous friction, ensured the biomass of sulphate reducing bacteria, biological active filling material processing efficiency is high, stable performance.
In order to achieve the above object, the present invention has adopted 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 to be fixedly bonded together by the limit of multi-disc net slice shape structured material the star structure forming, the embedding body that wherein forms the involved thalline of twine of net slice shape structured material mesh passes through mesh embedding, thereby form 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 taking polyethylene, polyvinyl chloride, polypropylene, ABS resin material as main, the water wetted materials such as the polyvinyl alcohol (PVA) of interpolation 6wt%-9wt%, make netted slab organization by modes such as strand hot melt molding or sheet material hot pressing pore-formings, its mesh shape can be circle, rhombus, square, rectangle.The preferably string diameter 0.5-2mm of 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, comprises 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), make the reticulated structure carrier of sheet shape 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 in 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, for example: can use three, four, five, six mesh carriers, make angle and be respectively 120 °, 90 °, 72 °, the multi-form stellate reticulum carrier of 60 °,
(2) sulphate reducing bacteria concentrated solution and polyvinyl alcohol solution are mixed, 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, put into after saturated boric acid solution 1-3h, regulate boric acid solution pH to 8-10, crosslinked 3-24h, taken out, cleaned remained on surface material, obtained sulfate reduction bacteria immobilization star biological active filling material.
The addition of polyvinyl alcohol in carrier (PVA) can suitably be adjusted as required, and this is prior art, and the quality percentage composition 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 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, and embedding body difficult drop-off makes the biological active filling material resistance to overturning that makes good, is conducive to the sulfate reduction bacteria biomass that keeps higher;
2. mesh carrier is designed to star, and this structure has ensured that the embedding body between biological active filling material fin can not be subject to extraneous friction, is conducive to the higher sulfate reduction bacteria biomass of maintenance, and biological active filling material processing efficiency is high, stable performance;
3. experimental study shows, taking conventional filler as the carrier immobilized biological active filling material poor stability obtaining, in 2 days, embedded material almost all comes off, and the biological active filling material resistance to overturning obtaining 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 makes, 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, has added the water wetted materials such as polyvinyl alcohol (PVA), has improved the wetting ability of carrier, has increased the intensity of carrier and embedding body bonding, has improved overall stability;
6. when biological active filling material makes embedding body can implementation structure thickness less due to the existence of mesh skeleton structure, strengthened again 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, cannot realize good carrier performance if make thickness like this with embedding body self material in water technology processing unit;
7. the crosslinked fixing polyvinyl alcohol-boric acid secondary crosslinking method that adopts of embedding body, can effectively reduce biomass loss, is conducive to keep 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 is all covered by embedding body, and embedding body structure is thinner in addition, is conducive to sulphate reducing bacteria contact substrate, has avoided the waste of material simultaneously, effectively raises the utilization ratio of carrier filler.
Brief description of the drawings
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. embedding 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 to this.
Embodiment 1
1. the preparation of mesh carrier
Taking high molecular polymers such as polypropylene as main raw, add the polyvinyl alcohol (PVA) of 6wt%, system is grown into 1.0cm, and wide is the sheet shape mesh carrier of 0.7cm.Mesh is shaped as square, and the length of side is 2mm, and string diameter is 1.5mm.The stellate reticulum carrier that six above-mentioned shape carriers are spent by hot melt, bonding formation angle 60.
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. the preparation of embedding liquid
Weighing polyvinyl alcohol 5kg, adds 25L ultrapure water post-heating to 85 DEG C, dissolves 15min.The polyvinyl alcohol solution of dissolving is taken out and stir after reheat 5min, after stirring, be cooled to 31 ± 1 DEG C.25L polyvinyl alcohol solution and the 25L sulphate reducing bacteria concentrated solution preparing mix, and add 1.3kg calcium carbonate, make 50L embedding liquid after stirring.
4. the combination of embedding liquid and mesh carrier
Embedding liquid is uniformly coated on to mesh carrier surface, guarantees that mesh carrier surface is all by embedding liquid uniform fold.
5. the preparation of sulphate reducing bacteria biological active filling material
The mesh carrier of smearing embedding liquid in step (4) is put into saturated boric acid solution, make it in submerged condition, leave standstill 3h crosslinked, regulator solution pH to 9.0, standing 4h completes fixing, clean, 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%, water temperature is 24 DEG C-26 DEG C, HRT=12h, pH is 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 in reactor in precipitation state, 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 stable.SO in water outlet
4 2-concentration is 69-93mg/L, and clearance remains on more than 90%, and reactor moves 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
Taking high molecular polymers such as polyethylene as main raw, add the polyvinyl alcohol (PVA) of 5wt%, system is grown into 1.0cm, and wide is the sheet shape mesh carrier of 0.7cm.Mesh is shaped as square, and the length of side is 2mm, and string diameter is 1.5mm.The stellate reticulum carrier that six above-mentioned shape carriers are spent by hot melt, bonding formation angle 60.
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. the preparation of embedding liquid
Weighing polyvinyl alcohol 5kg, adds 25L ultrapure water post-heating to 85 DEG C, dissolves 15min.The polyvinyl alcohol solution of dissolving is taken out and stir after reheat 5min, after stirring, be cooled to 31 ± 1 DEG C.25L polyvinyl alcohol solution and the 25L sulphate reducing bacteria concentrated solution preparing mix, and add 1kg calcium carbonate, make 50L embedding liquid after stirring.
4. the combination of embedding liquid and mesh carrier
Embedding liquid is uniformly coated on to mesh carrier surface, guarantees that mesh carrier surface is all by embedding liquid uniform fold.
5. the preparation of sulphate reducing bacteria biological active filling material
The mesh carrier of smearing embedding liquid in step (4) is put into saturated boric acid solution, make it in submerged condition, leave standstill 3h crosslinked, regulator solution pH to 9.0, standing 4h completes immobilization, clean, 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%, water temperature is 24 DEG C-26 DEG C, HRT=8h, pH is 7.5-8.0, ORP≤-310mV, using Sodium.alpha.-hydroxypropionate as organic carbon source, SO
4 2-concentration is 2000 ± 15mg/L left and right, ensures COD/SO
4 2->=2.Reactor increases the upflow velocity of water by effluent recycling mode, make biological active filling material in reactor in fluidized state.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 stable.Water outlet SO
4 2-concentration is 148-197mg/L, and clearance remains on more than 90%.Reactor moves 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 the biological active filling material resistance to overturning that makes 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 to be fixedly bonded together by the limit of multi-disc net slice shape structured material the star structure forming, the twine that wherein forms net slice shape structured material mesh is passed through mesh embedding by the embedding body of Containing Sulfate Reducing Bacteria, thereby form overall rivet clasp structure, embedding body forms millimetre-sized membrane structure on netted slab organization.
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 taking polyethylene, polyvinyl chloride, polypropylene, ABS resin material as main, add polyvinyl alcohol (PVA) water wetted material, make netted slab organization by modes such as strand hot melt molding or sheet material hot pressing pore-formings, its mesh is shaped as circle, rhombus, square, rectangle, the string diameter 0.5-2mm of mesh.
4. the method for any sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier described in preparation claim 1-3, is characterized in that, comprises the following steps:
(1) taking macromolecular materials such as polyethylene, polyvinyl chloride, polypropylene, ABS resin as main, add the water wetted materials such as polyvinyl alcohol (PVA), make the reticulated structure carrier of sheet shape by modes such as strand hot melt or sheet material hot pressing pore-formings, long is 0.5-3cm, wide is 0.5-3cm, the limit of the reticulated structure carrier of some shapes is fixedly bonded together by hot melt extruded, the mode such as bonding, and the angle of arbitrary two adjacent sheet shape carriers is identical, makes multi-form stellate reticulum carrier;
(2) sulphate reducing bacteria concentrated solution and polyvinyl alcohol solution are mixed, 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, put into after saturated boric acid solution 1-3h, regulate boric acid solution pH to 8-10, crosslinked 3-24h, taken out, cleaned remained on surface material, obtained sulfate reduction bacteria immobilization star biological active filling material.
5. any sulfate reduction bacteria immobilization star biological active filling material based on mesh carrier described in claim 1-3 is for water treatment.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699186A (en) * | 1992-09-18 | 1994-04-12 | Ngk Insulators Ltd | Production of carrier for immobilization |
| 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 |
| 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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2014
- 2014-04-04 CN CN201410137278.3A patent/CN103951032B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699186A (en) * | 1992-09-18 | 1994-04-12 | Ngk Insulators Ltd | Production of carrier for immobilization |
| 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 |
| 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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