CN103951072B - A kind of sulfur-oxidizing bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier - Google Patents
A kind of sulfur-oxidizing bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
Based on a sulfur-oxidizing 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 sulfur-oxidizing 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 sulfur-oxidizing bacteria biological active filling material.Biological active filling material prepared by the present invention, not only effectively can solve the problems such as poor, the easy loss of sulfur-oxidizing bacteria adhesive ability, can also improve reactor for treatment ability, shorten start time.
Description
Technical field
The invention belongs to water treatment field, particularly a kind of sulfur-oxidizing bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier.
Background technology
Along with the fast development of China's industry, in the industries such as oil refining, coking, pharmacy and petrochemical complex, the waste water of sulfur compound is often had to discharge in a large number.Process at present for Sulfide in water roughly comprises physico-chemical process and biological oxidation process, and biological oxidation process due to have without the need to add chemical agent, removal efficiency high, produce the advantages such as biological sludge amount is few, non-secondary pollution, progressively become main method and the research emphasis of sulfur-containing waste water process.When utilizing the biological metabolism function of sulfur-oxidizing bacteria to process sulfur-containing waste water, usually because water inlet sulfide concentration is high, the Metabolic activity of the functional microorganism in reactor is suppressed, functional microorganism is caused to need the adaptive phase grown very much, and due to the adhesion property of sulfur-oxidizing bacteria not strong, very easily run off, so high density sulfur-oxidizing bacteria concentration will be kept in the reactor also very not easily with water outlet.In recent years, many scholars start to adopt the form of biofilm to attempt the biomass keeping sulfur-oxidizing bacteria in reactor, but due to the limitation of conventional filler, produce little effect in actual waste water process practice.So some scholars start the immobilization technology of sulfur-oxidizing bacteria.
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 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 sulfur-oxidizing 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 sulfur-oxidizing 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 sulfur-oxidizing 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 sulfur-oxidizing 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 macromolecular material, adding mass percent is 6%-9% hydrophilizing agent polyvinyl alcohol (PVA), 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 sulfur-oxidizing bacteria immobilization star biological active filling material based on mesh carrier, is characterized in that, comprise the following steps:
(1) based on polyethylene, polyvinyl chloride, polypropylene, ABS resin material, adding mass percent is 6%-9% hydrophilizing agent polyvinyl alcohol (PVA), made 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, and 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, the angle of arbitrary two adjacent sheet shape carriers is identical, make multi-form stellate reticulum carrier, such as: three, four, five, six mesh carriers can be used, the multi-form stellate reticulum carrier that angle is respectively 120 °, 90 °, 72 °, 60 ° is made;
(2) by sulfur-oxidizing 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 sulfur-oxidizing 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%.
Above-mentioned a kind of sulfur-oxidizing bacteria immobilization star biological active filling material based on mesh carrier is used for water treatment.
The beneficial effect of the sulfur-oxidizing 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 sulfur-oxidizing bacteria concentration;
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 sulfur-oxidizing bacteria concentration, 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 sulfur-oxidizing bacteria biological active filling material that immobilization is obtained, global density between 0.85-1.10, can be made into floated or floatation type, can make the biological active filling material with certain function 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, the loss of bacterium can be effectively reduced, be conducive to the quantity keeping bacterial activity and active function microorganism;
8. the sulfur-oxidizing bacteria bag bacterium amount of immobilized biological activated filler is large, and sulfur-oxidizing bacteria 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 sulfur-oxidizing bacteria contact substrate, avoid the waste of material simultaneously, effectively raise the utilization ratio of carrier filler.
Accompanying drawing explanation
Fig. 1 is star sulfur-oxidizing 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 sulfur-oxidizing 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 polypropylene high molecular polymer for main raw, add the water wetted material polyvinyl alcohol (PVA) that massfraction is 6%, 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 1.0mm.By the stellate reticulum carrier of six sheet above shape carriers by hot melt, bonding formation angle 60 degree.
2. the preparation of sulfur-oxidizing bacteria concentrated solution
By the sulfur-oxidizing bacteria bacteria suspension centrifugal concentrating after amplification cultivation, obtain 3.5 × 10
9the concentrated solution of the sulfur-oxidizing bacteria of individual/mL.
3. embed the preparation of liquid
Weighing polyvinyl alcohol 10kg, adds 50L 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 again.50L polyvinyl alcohol solution and the 50L sulfur-oxidizing bacteria concentrated solution mixing prepared, and add 1.8kg calcium carbonate, namely make 100L 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 sulfur-oxidizing bacteria biological active filling material
The mesh carrier smearing embedding liquid in step (4) is put into saturated boric acid solution, makes it be in submerged condition, leave standstill 3h, regulator solution pH to 9.0, standing 4h completes immobilization, cleaning, obtain sulfur-oxidizing bacteria biological active filling material, this biological active filling material proportion is between 0.95-1.00.
6. the application of sulfur-oxidizing bacteria biological active filling material activity
To 1m
3reactor in add embedded star biological active filling material, filling ratio is 60%, and water temperature is 24 DEG C-26 DEG C, and HRT=0.4h, DO are 1.0-4.0mg/L, and adopt the water outlet of sulfate reduction device as water inlet, sulfide concentration is 350 ~ 390mg/L.Biological active filling material becomes levitated state under aeration air supporting effect, every day assaying reaction device sweetening effectiveness.Water outlet detected result shows, reactor runs to the 8th day, and sweetening effectiveness is stablized, the mean concns of water outlet sulfide is 10.4 ~ 22.6mg/L, and clearance remains on more than 94%, and reactor runs 1 year continuously, reactor organisms sweetening effectiveness is stablized, and the percentage of head rice of biological active filling material reaches 92%.
Embodiment 2
1. the preparation of mesh carrier
With polypropylene high molecular polymer for main raw, add the water wetted material polyvinyl alcohol (PVA) that massfraction is 6%, 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 1.0mm.By the stellate reticulum carrier of six sheet above shape carriers by hot melt, bonding formation angle 60 degree.
2. the preparation of sulfur-oxidizing bacteria concentrated solution
By the sulfur-oxidizing bacteria bacteria suspension centrifugal concentrating after amplification cultivation, obtain 3.5 × 10
9the concentrated solution of the sulfur-oxidizing bacteria of individual/mL.
3. embed the preparation of liquid
Weighing polyvinyl alcohol 10kg, adds 50L 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 again.50L polyvinyl alcohol solution and the 50L sulfur-oxidizing bacteria bacteria suspension mixing prepared, and add 2kg calcium carbonate, namely make 100L 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 sulfur-oxidizing bacteria biological active filling material
The mesh carrier smearing embedding liquid in step (4) is put into saturated boric acid solution, makes it be in submerged condition, leave standstill 3h, regulator solution pH to 9.0, standing 4h completes immobilization, cleaning, obtain sulfur-oxidizing bacteria biological active filling material, this biological active filling material proportion is between 0.95-1.05.
6. the application of sulfur-oxidizing bacteria biological active filling material
To 1m
3reactor in add embedded star biological active filling material, filling ratio is 60%, and water temperature is 24 DEG C-26 DEG C, and HRT=0.4h, DO are 1.0-4.0mg/L, and adopt the water outlet of sulfate reduction device as water inlet, sulfide concentration is 350 ~ 390mg/L.Reactor increases the upflow velocity of water by effluent recycling mode, makes biological active filling material become suspension fluidization state under the dual function of aeration with Hydraulic Circulation, every day assaying reaction device sweetening effectiveness.Water outlet detected result shows, reactor runs to the 7th day, and sweetening effectiveness is stablized, and the mean concns of water outlet sulfide is 9.6 ~ 18.5mg/L, and clearance remains on 95%
Above, reactor runs 1 year continuously, and reactor organisms sweetening effectiveness is stablized, and the percentage of head rice of filler reaches 94%.Above-mentioned example shows, sulfur-oxidizing bacteria immobilization star biological active filling material operating process based on mesh carrier is simple, embedding body and carrier form overall rivet clasp structure by mesh and carrier, make the biological active filling material resistance to overturning that obtains good, embed body difficult drop-off, bacterial concentration is higher.
Claims (5)
1. prepare a kind of method of the sulfur-oxidizing 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 containing sulfur-oxidizing bacteria, thus forming overall rivet clasp structure, embedding body forms millimetre-sized membrane structure on netted slab organization; 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 sulfur-oxidizing 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 sulfur-oxidizing bacteria immobilization star biological active filling material.
2. according to the method for claim 1, it is characterized in that: net slice shape structured material is long is 0.5-3cm, and wide is 0.5-3cm.
3. according to the method for claim 1, it is characterized in that: netted slab organization, its mesh form is the string diameter 0.5-2mm of circle, rhombus, rectangle, mesh.
4. according to the sulfur-oxidizing bacteria immobilization star biological active filling material based on mesh carrier that any one method of claim 1-3 prepares.
5. the sulfur-oxidizing bacteria immobilization star biological active filling material based on mesh carrier prepared according to any one method of claim 1-3 is 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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| 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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