CN103159330A - Porous light-weight carbon-based biological carrier and preparation method thereof - Google Patents
Porous light-weight carbon-based biological carrier and preparation method thereof Download PDFInfo
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- CN103159330A CN103159330A CN2013101175314A CN201310117531A CN103159330A CN 103159330 A CN103159330 A CN 103159330A CN 2013101175314 A CN2013101175314 A CN 2013101175314A CN 201310117531 A CN201310117531 A CN 201310117531A CN 103159330 A CN103159330 A CN 103159330A
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Abstract
The invention provides a porous light-weight carbon-based biological carrier. The porous light-weight carbon-based biological carrier is a foamed coke powder/polyvinyl alcohol gel mixture which is prepared by performing crosslinking reaction on coke powder, a polyvinyl alcohol solution, a foaming agent solution and a crosslinking agent solution used as raw materials at normal temperature, wherein the weight percent concentration of the polyvinyl alcohol solution is 5-15%; the weight percent concentration of the foaming agent solution is 0.2-2%; the weight percent concentration of the crosslinking agent solution is 0.5-1.5%; the weight ratio of the polyvinyl alcohol water solution to the coke powder is (10-25):1; the weight ratio of the polyvinyl alcohol water solution to the foaming agent solution is (15-45):1; and the weight ratio of the polyvinyl alcohol water solution to the crosslinking agent solution is (20-50):1. The biological carrier is high in film-forming speed and microbial capacity, provides a proper nutrient source for microorganisms and has no harm to the environment. Meanwhile, the invention also provides a preparation method of the porous light-weight carbon-based biological carrier. The preparation method has the advantages of simple process, less required equipment and low preparation cost.
Description
Technical field
The invention belongs to biomembrance process and process the waste water technology field, specifically refer to a kind of porous light charcoal base bio-carrier and preparation method thereof.
Background technology
Wastewater Treated by Activated Sludge Process waste water has technical maturity, the advantages such as operation, maintenance cost is low are that domestic water is processed the most frequently used method, but the activated sludge process floor space is large, excess sludge is many, denitrification effect is poor, the shortcomings such as sludge bulking and sludge loss easily occur, and people just adopt biomembrance process to carry out wastewater biochemical and process.The advantages such as since the successful operation of biological filter tank, biomembrance process is strong because of degradation capability, and duration of contact is short, and the little and cost of investment of floor space is low are able to fast-developing the application in recent years.And determined water treatment effect and mass-transfer efficiency in reactor as microbial carrier material in biomembrance process.Therefore, bio-carrier is the core of biomembrance process water technology.In treating processes, the absorption between biology and bio-carrier, not only relevant with the characteristic of biology in conjunction with tightness degree also closely is connected with the bio-carrier material property.Therefore, the surface property of bio-carrier, voidage, specific surface area and material have material impact to the absorption of biology, mass transfer and the water treatment capacity of carrier.On domestic market, the material that can be used for bio-carrier common are inorganic materials (as pottery, rubble, slag, zeolite, gac etc.) and reaches synthetic organic-inorganic macromolecular material etc. to organic polymer material (as industrial plastic, as polyethylene, polypropylene, polyvinyl chloride, polyphenyl alkene and various resins etc.).And in actual industrial application process, not only to consider the performance (physical strength, stability, Biostatic, close hydrophobic nature etc.), specific surface area of bio-carrier, biological consistency etc., also need to consider the factors such as the drawing materials of material, cost value, manufacturing conditions.There are many shortcomings in existing common bio-carrier, as high in material cost, complete processing is complicated, also there are the environmental problems such as secondary pollution in part, such as the inorganic ceramic material that adopts, ubiquity density is large, porosity is low, specific surface area is little and reactor in the shortcomings such as the fluidization power consumption is large; Most polymer organic carrier comes from the petrochemical industry derived product, and as polypropylene, polyethylene etc., their wetting ability is poor, and microorganism colonization, microbial biomass etc. are relatively poor, and the photodissociation in environment of part material, even environmental organism are had certain toxicity.
Summary of the invention
Purpose of the present invention is exactly to overcome the deficiency that existing bio-carrier exists, a kind of porous light charcoal base bio-carrier and preparation method thereof is provided, not only film forming is fast, the microorganism capacity is large for this bio-carrier, also for microorganism provides suitable nutrition source, and environmental sound.
For achieving the above object, porous light charcoal base bio-carrier of the present invention, its special character is: it is to be crosslinking reaction that raw material occurs the at normal temperatures coke powder that obtains foaming/polyvinyl alcohol gel mixture by coke powder, polyvinyl alcohol solution, foaming agent solution, cross-linking agent solution, wherein, the weight percent concentration of described polyvinyl alcohol solution is 5～15%; The weight percent concentration of foaming agent solution is 0.2～2%; The weight percent concentration of cross-linking agent solution is 0.5～1.5%, the weight ratio of described polyvinyl alcohol water solution and coke powder is 10～25: 1, the weight ratio of polyvinyl alcohol water solution and foaming agent solution is 15～45: 1, and the weight ratio of polyvinyl alcohol water solution and cross-linking agent solution is 20～50: 1.
Preferably, described whipping agent is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate, and described linking agent is a kind of in glutaraldehyde, formaldehyde or oxalic dialdehyde.
The present invention also will provide the preparation method of described porous light charcoal base bio-carrier, and its special character is: this preparation method comprises the following steps successively:
1) be at first, 5～15% polyvinyl alcohol water solution with the water-soluble weight percentage that is configured to of polyvinyl alcohol;
2), secondly getting coke powder, to put into weight percent concentration be that 10～50% salpeter solution carries out oxidation modification and processes, and processes after 2～5h the coke powder washing to neutral; The water-wet behavior that can effectively increase coke powder is processed in this oxidation modification, also removes the part inorganics in coke powder simultaneously;
3), then coke powder is carried out drying treatment;
4) be, that 0.2～2% whipping agent, weight percent concentration are that 0.5～1.5% cross-linking agent solution adds in described polyvinyl alcohol water solution again with dried coke powder, weight percent concentration, stir 2～5h, the coke powder that obtains foaming/polyvinyl alcohol gel mixture; The weight ratio of wherein said polyvinyl alcohol water solution and coke powder is 10～25: 1, and the weight ratio of polyvinyl alcohol water solution and foaming agent solution is 15～45: 1, and the weight ratio of polyvinyl alcohol water solution and cross-linking agent solution is 20～50: 1;
5), then described coke powder/polyvinyl alcohol gel mixture is dried after knifing, curtain coating are processed and obtain coke powder/polyvinyl alcohol gel film;
6), then coke powder/polyvinyl alcohol gel film is carried out heat modification and process, described heat modification treatment process is to be placed in the baking oven of 80～150 ℃ to toast 1～2h;
7), at last coke powder/polyvinyl alcohol gel film is carried out stripping and slicing, granulation as required, namely get porous light carbon back microbe carrier.
Preferably, the polymerization degree of polyvinyl alcohol described in step 1) is greater than 1750.
Further, the coke powder granularity step 2) is 180～300 orders.
Also further, the drying treatment described in step 3) is freeze-day with constant temperature 1～2h under 80～100 ℃ of conditions;
Further, the linking agent described in step 4) is a kind of in glutaraldehyde, formaldehyde or oxalic dialdehyde.
Again further, the whipping agent described in step 4 is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate.
because the matrix of porous light charcoal base bio-carrier of the present invention is mainly polyvinyl alcohol and skeleton carbonaceous material, add the effect of whipping agent, the porous colloidalmaterial that forms on carbonaceous material, therefore, have than bigger serface and good absorption property, can improve carrier to adsorptive power and the biofilm amount of microorganism and pollutent, and then be conducive to adapt to the processing of high concentrated organic wastewater, and has a higher anti impulsion load ability, microorganism the porosity biofilm not only easily and also quantity many, biological capacity is large, in addition, polyvinyl alcohol material is good degradable biomaterial, nontoxic to microorganism and environment.From biological aspect, polyvinyl alcohol is dissolved in the aqueous solution, in the not enough situation of carbon source, can be used as microbe carbon source.This microbe carrier is drawn materials conveniently, good to bioaffinity, can be to environment, discarded carrier in system's operational process enters biochemical sludge, can deliver to coal yard coal blending workshop and use as raw material or raw materials for sintering, the resource utilization method of a kind of economic, practical, the high added value that also provides for the low value coke powder.The present invention is by controlling the weight ratio of each component raw material of porous light charcoal base bio-carrier, density, the porosity of different ratios biofilm carrier have effectively namely been guaranteed, also guarantee the life-span of biofilm carrier in the aqueous solution, especially to water-soluble polyvinyl alcohol preferably.And preparation method's technique of the present invention is simple, and required equipment is few, and preparation cost is low.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of a kind of porous light charcoal base bio-carrier of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, porous light charcoal base bio-carrier of the present invention and preparation method thereof is described in further detail.
Embodiment one
A kind of porous light charcoal base bio-carrier, it is to prepare according to following steps:
1) be, at first that 1750 polyvinyl alcohol is dissolved in return stirring 8h in the 85ml boiling water of 100 ℃ with the 15g polymerization degree, obtain weight percent and be 15% polyvinyl alcohol solution;
2), secondly get particle diameter 300 purpose coke powders and put into that under room temperature, weight percent concentration is that 50% salpeter solution carries out oxidation modification, process 2h, take out and be washed till neutrality, then clean 3 times with tap water;
3), then with coke powder under 100 ℃ of conditions in baking oven constant temperature drying 2h;
4) be that 0.5% lauryl sodium sulfate aqueous solution 5ml and weight percent concentration are rapid stirring 2h in the polyvinyl alcohol solution of 0.5% the glutaraldehyde water solution 2ml 100ml that is added to step 1), again with 5g coke powder, weight percent concentration, get the coke powder of foaming/polyvinyl alcohol solution gel mixture;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass, after knifing, curtain coating are processed, dries under room temperature and obtain coke powder/polyvinyl alcohol gel film;
6), then will obtain the baking oven that coke powder/polyvinyl alcohol gel film is placed in 150 ℃ and carry out the 1h heat modification;
7) be cut into as required bulk after, at last coke powder/polyvinyl alcohol gel film being cooled to room temperature, namely get porous light carbon back microbe carrier.
After testing, after the prepared finished product porous light charcoal base bio-carrier drying of the present embodiment method, density is 0.57g/cm
3, density is about 1.1g/cm in solution
3, under the solution disturbance, can be suspended in solution.In utilizing the experiment of fluidized bed bio membrane reactor Treatment of Wastewater in Coking, at hydraulic detention time (HRT) 55h, record its chemical oxygen demand (COD) (COD) and surpass 98%, approximately do not improved 41% than adding bio-carrier; Its total nitrogen (TN) clearance surpasses 67%, has not approximately improved 39% than adding bio-carrier.
Embodiment two
A kind of porous light charcoal base bio-carrier, it is to prepare according to following steps:
1) be, at first that 1850 polyvinyl alcohol is dissolved in return stirring 8h in the 90ml boiling water of 100 ℃ with the 10g polymerization degree, obtain weight percent and be 10% polyvinyl alcohol solution;
2), secondly get particle diameter 180 purpose coke powders and put into that under room temperature, weight percent concentration is that 30% salpeter solution carries out oxidation modification, process 3h, take out and be washed till neutrality, then clean 4 times with tap water;
3), then with coke powder under 90 ℃ of conditions in baking oven constant temperature drying 1.5h;
4) be that 1.0% lauryl sodium sulfate aqueous solution 5ml and weight percent concentration are rapid stirring 3h in the polyvinyl alcohol solution of 1.0% the glutaraldehyde water solution 2ml 100ml that is added to step 1), again with 10g coke powder, weight percent concentration, get the coke powder of foaming/polyvinyl alcohol solution gel mixture;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass, after knifing, curtain coating are processed, dries under room temperature and obtain coke powder/polyvinyl alcohol gel film;
6), then will obtain the baking oven that coke powder/polyvinyl alcohol gel film is placed in 120 ℃ and carry out the 1.5h heat modification;
7) be cut into as required bulk after, at last coke powder/polyvinyl alcohol gel film being cooled to room temperature, namely get porous light carbon back microbe carrier.
After testing, after the prepared finished product porous light charcoal base bio-carrier drying of the present embodiment method, density is 0.63g/cm
3, density is about 1.16g/cm in solution
3, under the solution disturbance, can be suspended in solution.In utilizing the experiment of fluidized bed bio membrane reactor Treatment of Wastewater in Coking, at hydraulic detention time (HRT) 45h, record its chemical oxygen demand (COD) (COD) and surpass 95%, approximately do not improved 30% than adding bio-carrier; Its total nitrogen (TN) clearance surpasses 55%, has not approximately improved 32% than adding bio-carrier.
Embodiment three
A kind of porous light charcoal base bio-carrier, it is to prepare according to following steps:
1) be, at first that 1900 polyvinyl alcohol is dissolved in return stirring 8h in the 95ml boiling water of 100 ℃ with the 5g polymerization degree, obtain weight percent and be 5% polyvinyl alcohol solution;
2), secondly get particle diameter 200 purpose coke powders and put into that under room temperature, weight percent concentration is that 10% salpeter solution carries out oxidation modification, process 5h, take out and be washed till neutrality, then clean 3 times with tap water;
3), then with coke powder under 90 ℃ of conditions in baking oven constant temperature drying 2h;
4) be that 2.0% lauryl sodium sulfate aqueous solution 5ml and weight percent concentration are rapid stirring 4h in the polyvinyl alcohol solution of 1.5% the glutaraldehyde water solution 2ml 100ml that is added to step 1), again with 5g coke powder, weight percent concentration, get the coke powder of foaming/polyvinyl alcohol solution gel mixture;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass, after knifing, curtain coating are processed, dries under room temperature and obtain coke powder/polyvinyl alcohol gel film;
6), then will obtain the baking oven that coke powder/polyvinyl alcohol gel film is placed in 80 ℃ and carry out the 1.5h heat modification;
7) be cut into as required bulk after, at last coke powder/polyvinyl alcohol gel film being cooled to room temperature, namely get porous light carbon back microbe carrier.
After testing, after the prepared finished product porous light charcoal base bio-carrier drying of the present embodiment method, density is 0.75g/cm
3, density is about 1.23g/cm in solution
3, under the solution disturbance, can be suspended in solution.In utilizing the experiment of fluidized bed bio membrane reactor Treatment of Wastewater in Coking, at hydraulic detention time (HRT) 45h, record its chemical oxygen demand (COD) (COD) and surpass 94%, approximately do not improved 27% than adding bio-carrier; Its total nitrogen (TN) clearance surpasses 53%, has not approximately improved 31% than adding bio-carrier.
The scanning electron microscope (SEM) photograph of the porous light charcoal base bio-carrier of above-mentioned three embodiment, accompanying drawing shows that this bio-carrier is good porous membrane structure.
Claims (9)
1. porous light charcoal base bio-carrier, it is characterized in that: it is to be the raw material coke powder that crosslinking reaction occurs at normal temperatures obtains foaming/polyvinyl alcohol gel mixture by coke powder, polyvinyl alcohol solution, foaming agent solution, cross-linking agent solution, wherein, the weight percent concentration of described polyvinyl alcohol solution is 5～15%; The weight percent concentration of foaming agent solution is 0.2～2%; The weight percent concentration of cross-linking agent solution is 0.5～1.5%, the weight ratio of described polyvinyl alcohol water solution and coke powder is 10～25: 1, the weight ratio of polyvinyl alcohol water solution and foaming agent solution is 15～45: 1, and the weight ratio of polyvinyl alcohol water solution and cross-linking agent solution is 20～50: 1.
2. porous light charcoal base bio-carrier according to claim 1, it is characterized in that: described whipping agent is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate, described linking agent is a kind of in glutaraldehyde, formaldehyde or oxalic dialdehyde.
3. the preparation method of the described porous light charcoal of claim 1 a base bio-carrier, it is characterized in that: this preparation method comprises the following steps successively:
1) be at first, 5～15% polyvinyl alcohol water solution with the water-soluble weight percentage that is configured to of polyvinyl alcohol;
2), secondly getting coke powder, to put into weight percent concentration be that 10～50% salpeter solution carries out oxidation modification and processes, and processes after 2～5h the coke powder washing to neutral;
3), then coke powder is carried out drying treatment;
4) be, that 0.2～2% whipping agent, weight percent concentration are that 0.5～1.5% cross-linking agent solution adds in described polyvinyl alcohol water solution again with dried coke powder, weight percent concentration, stir 2～5h, the coke powder that obtains foaming/polyvinyl alcohol gel mixture; The weight ratio of wherein said polyvinyl alcohol water solution and coke powder is 10～25: 1, and the weight ratio of polyvinyl alcohol water solution and foaming agent solution is 15～45: 1, and the weight ratio of polyvinyl alcohol water solution and cross-linking agent solution is 20～50: 1;
5), then described coke powder/polyvinyl alcohol gel mixture is dried after knifing, curtain coating are processed and obtain coke powder/polyvinyl alcohol gel film;
6), then coke powder/polyvinyl alcohol gel film is carried out heat modification and process, described heat modification treatment process is to be placed in the baking oven of 80～150 ℃ to toast 1～2h;
7), at last coke powder/polyvinyl alcohol gel film is cooled to room temperature, carry out as required stripping and slicing, granulation, namely get porous light carbon back microbe carrier.
4. the preparation method of porous light charcoal base bio-carrier according to claim 3, it is characterized in that: the polymerization degree of polyvinyl alcohol described in step 1) is greater than 1750.
5. the preparation method of according to claim 3 or 4 described porous light charcoal base bio-carriers, is characterized in that: step 2) described in the coke powder granularity be 180～300 orders.
6. the preparation method of according to claim 3 or 4 described porous light charcoal base bio-carriers, it is characterized in that: the drying treatment described in step 3) is freeze-day with constant temperature 1～2h under 80～100 ℃ of conditions.
7. the preparation method of according to claim 3 or 4 described porous light charcoal base bio-carriers is characterized in that: the linking agent described in step 4) is a kind of in glutaraldehyde, formaldehyde or oxalic dialdehyde.
8. the preparation method of according to claim 3 or 4 described porous light charcoal base bio-carriers, it is characterized in that: the whipping agent described in step 4 is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate.
9. the preparation method of porous light charcoal base bio-carrier according to claim 7, it is characterized in that: the whipping agent described in step 4) is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate.
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| CN103408097A (en) * | 2013-08-27 | 2013-11-27 | 武汉钢铁(集团)公司 | Method for removing sulfides in coking wastewater |
| CN104628123A (en) * | 2015-01-28 | 2015-05-20 | 苏州赛华仪控股份有限公司 | Modified biological slag microbial carrier and preparation method thereof |
| CN106360095A (en) * | 2016-10-13 | 2017-02-01 | 常州市鼎升环保科技有限公司 | Preparation method for feed additive for promoting silkie digestion |
| CN108892231A (en) * | 2018-07-23 | 2018-11-27 | 南京顺水达环保科技有限公司 | A kind of biological reinforced membrane reactor, manufacturing method and its purposes in Treatment of Coking Effluent |
| CN111439824A (en) * | 2020-03-06 | 2020-07-24 | 浙江正洁环境科技有限公司 | Water treatment biofilm carrier with bacteria promoting performance and preparation method and application thereof |
| CN114365673A (en) * | 2022-02-21 | 2022-04-19 | 中国林业科学研究院生态保护与修复研究所 | Preparation method of composite organic high water-holding culture substrate material |
| CN116786094A (en) * | 2023-07-26 | 2023-09-22 | 山东省煤田地质规划勘察研究院 | Sewage plant tail water advanced nitrogen and phosphorus removal filler based on water supply plant sludge, preparation method and sewage plant tail water advanced treatment system |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106360095A (en) * | 2016-10-13 | 2017-02-01 | 常州市鼎升环保科技有限公司 | Preparation method for feed additive for promoting silkie digestion |
| CN108892231A (en) * | 2018-07-23 | 2018-11-27 | 南京顺水达环保科技有限公司 | A kind of biological reinforced membrane reactor, manufacturing method and its purposes in Treatment of Coking Effluent |
| CN108892231B (en) * | 2018-07-23 | 2021-06-01 | 南京顺水达环保科技有限公司 | Method for manufacturing biological enhanced membrane reactor and application of reactor in coking wastewater treatment |
| CN111439824A (en) * | 2020-03-06 | 2020-07-24 | 浙江正洁环境科技有限公司 | Water treatment biofilm carrier with bacteria promoting performance and preparation method and application thereof |
| CN111439824B (en) * | 2020-03-06 | 2022-08-09 | 浙江正洁环境科技有限公司 | Water treatment biofilm carrier with bacteria promoting performance and preparation method and application thereof |
| CN114365673A (en) * | 2022-02-21 | 2022-04-19 | 中国林业科学研究院生态保护与修复研究所 | Preparation method of composite organic high water-holding culture substrate material |
| CN116786094A (en) * | 2023-07-26 | 2023-09-22 | 山东省煤田地质规划勘察研究院 | Sewage plant tail water advanced nitrogen and phosphorus removal filler based on water supply plant sludge, preparation method and sewage plant tail water advanced treatment system |
| CN116786094B (en) * | 2023-07-26 | 2023-12-29 | 山东省煤田地质规划勘察研究院 | Sewage plant tail water advanced nitrogen and phosphorus removal filler based on water supply plant sludge, preparation method and sewage plant tail water advanced treatment system |
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