CN103159330B - 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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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 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 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 processing.Since the successful operation of biological filter, biomembrance process because of degradation capability strong, duration of contact is short, and the little and cost of investment of floor space is low etc., and advantage is able to fast-developing application in recent years.And as microbial carrier material, determined water treatment effect and mass-transfer efficiency in reactor 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 biological characteristic in conjunction with tightness degree, is also closely connected with bio-carrier material property.Therefore, the surface property of bio-carrier, voidage, specific surface area and material have material impact to the mass transfer of biological absorption, carrier and water treatment capacity.On domestic market, the material that can be used for bio-carrier common are inorganic materials (as pottery, rubble, slag, zeolite, gac etc.) to organic polymer material (as industrial plastic, as polyethylene, polypropylene, polyvinyl chloride, polyphenyl alkene and various resins etc.) and synthetic organic-inorganic macromolecular material 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 is the environmental problems such as secondary pollution in part, such as the inorganic ceramic material adopting, ubiquity density is large, porosity is low, specific surface area is little and reactor in the shortcomings such as fluidization power consumption is large; Most polymer organic carrier comes from petrochemical industry derived product, and as polypropylene, polyethylene etc., their wetting ability is poor, and microorganism colonization, microbial biomass etc. are poor, and the photodissociation in environment of part material, even environmental organism are had to certain toxicity.
Summary of the invention
Object 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, 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 that the crosslinking reaction that raw material occurs at normal temperatures obtains the coke powder/polyvinyl alcohol gel mixture foaming 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) by the water-soluble weight percentage that is configured to of polyvinyl alcohol, be first, 5～15% polyvinyl alcohol water solution;
2), secondly getting coke powder, to put into weight percent concentration be that 10～50% salpeter solution carries out oxidation modification processing, processes after 2～5h 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 to drying treatment;
4) cross-linking agent solution that the whipping agent that is, 0.2～2% by dried coke powder, weight percent concentration again, weight percent concentration are 0.5～1.5% adds in described polyvinyl alcohol water solution, stir 2～5h, obtain coke powder/polyvinyl alcohol gel mixture of foaming; 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 and obtains coke powder/polyvinyl alcohol gel film after processing through knifing, curtain coating;
6), then coke powder/polyvinyl alcohol gel film is carried out to heat modification processing, described heat modification treatment process is to be placed in the baking oven of 80～150 ℃ to toast 1～2h;
7), finally coke powder/polyvinyl alcohol gel film is carried out to stripping and slicing, granulation as required, obtain 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 forming on carbonaceous material, therefore, have compared with bigger serface and good absorption property, can improve carrier to the adsorptive power of microorganism and pollutent and biofilm amount, and then be conducive to adapt to the processing of high concentrated organic wastewater, and there is higher anti impulsion load ability, microorganism 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 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 also providing for 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 been guaranteed, also guarantee the life-span of biofilm carrier in the aqueous solution, especially to water-soluble good polyvinyl alcohol.And preparation method's technique of the present invention is simple, required equipment is few, and preparation cost is low.
Accompanying drawing explanation
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 mono-
A porous light charcoal base bio-carrier, it is to prepare according to following steps:
1), the polyvinyl alcohol that is first 1750 by the 15g polymerization degree is dissolved in return stirring 8h in the 85ml boiling water of 100 ℃, obtains weight percent and be 15% polyvinyl alcohol solution;
2), secondly getting particle diameter 300 object coke powders, to put into weight percent concentration under room temperature be that 50% salpeter solution carries out oxidation modification, processes 2h, takes out and be washed till neutrality, then clean 3 times with tap water;
3), then by coke powder under 100 ℃ of conditions in baking oven constant temperature drying 2h;
4), the lauryl sodium sulfate aqueous solution 5ml that is 0.5% by 5g coke powder, weight percent concentration again and the weight percent concentration glutaraldehyde water solution 2ml that is 0.5% is added to rapid stirring 2h in the polyvinyl alcohol solution of 100ml of step 1), obtains coke powder/polyvinyl alcohol solution gel mixture of foaming;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass,, after knifing, curtain coating are processed, under room temperature, dries and obtain coke powder/polyvinyl alcohol gel film;
6), then the baking oven that obtains coke powder/polyvinyl alcohol gel film and be placed in 150 ℃ is carried out to 1h heat modification;
7) after, finally coke powder/polyvinyl alcohol gel film being cooled to room temperature, be cut into as required bulk, obtain porous light carbon back microbe carrier.
After testing, the prepared dry rear density of finished product porous light charcoal base bio-carrier of the present embodiment method is 0.57g/cm
3, in solution, density is about 1.1g/cm
3, under 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%, than adding bio-carrier, approximately do not improved 41%; Its total nitrogen (TN) clearance surpasses 67%, than adding bio-carrier, has not approximately improved 39%.
Embodiment bis-
A porous light charcoal base bio-carrier, it is to prepare according to following steps:
1), the polyvinyl alcohol that is first 1850 by the 10g polymerization degree is dissolved in return stirring 8h in the 90ml boiling water of 100 ℃, obtains weight percent and be 10% polyvinyl alcohol solution;
2), secondly getting particle diameter 180 object coke powders, to put into weight percent concentration under room temperature be that 30% salpeter solution carries out oxidation modification, processes 3h, takes out and be washed till neutrality, then clean 4 times with tap water;
3), then by coke powder under 90 ℃ of conditions in baking oven constant temperature drying 1.5h;
4), the lauryl sodium sulfate aqueous solution 5ml that is 1.0% by 10g coke powder, weight percent concentration again and the weight percent concentration glutaraldehyde water solution 2ml that is 1.0% is added to rapid stirring 3h in the polyvinyl alcohol solution of 100ml of step 1), obtains coke powder/polyvinyl alcohol solution gel mixture of foaming;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass,, after knifing, curtain coating are processed, under room temperature, dries and obtain coke powder/polyvinyl alcohol gel film;
6), then the baking oven that obtains coke powder/polyvinyl alcohol gel film and be placed in 120 ℃ is carried out to 1.5h heat modification;
7) after, finally coke powder/polyvinyl alcohol gel film being cooled to room temperature, be cut into as required bulk, obtain porous light carbon back microbe carrier.
After testing, the prepared dry rear density of finished product porous light charcoal base bio-carrier of the present embodiment method is 0.63g/cm
3, in solution, density is about 1.16g/cm
3, under 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%, than adding bio-carrier, approximately do not improved 30%; Its total nitrogen (TN) clearance surpasses 55%, than adding bio-carrier, has not approximately improved 32%.
Embodiment tri-
A porous light charcoal base bio-carrier, it is to prepare according to following steps:
1), the polyvinyl alcohol that is first 1900 by the 5g polymerization degree is dissolved in return stirring 8h in the 95ml boiling water of 100 ℃, obtains weight percent and be 5% polyvinyl alcohol solution;
2), secondly getting particle diameter 200 object coke powders, to put into weight percent concentration under room temperature be that 10% salpeter solution carries out oxidation modification, processes 5h, takes out and be washed till neutrality, then clean 3 times with tap water;
3), then by coke powder under 90 ℃ of conditions in baking oven constant temperature drying 2h;
4), the lauryl sodium sulfate aqueous solution 5ml that is 2.0% by 5g coke powder, weight percent concentration again and the weight percent concentration glutaraldehyde water solution 2ml that is 1.5% is added to rapid stirring 4h in the polyvinyl alcohol solution of 100ml of step 1), obtains coke powder/polyvinyl alcohol solution gel mixture of foaming;
5), then coke powder/polyvinyl alcohol gel mixture glue is poured on bright and clean sheet glass,, after knifing, curtain coating are processed, under room temperature, dries and obtain coke powder/polyvinyl alcohol gel film;
6), then the baking oven that obtains coke powder/polyvinyl alcohol gel film and be placed in 80 ℃ is carried out to 1.5h heat modification;
7) after, finally coke powder/polyvinyl alcohol gel film being cooled to room temperature, be cut into as required bulk, obtain porous light carbon back microbe carrier.
After testing, the prepared dry rear density of finished product porous light charcoal base bio-carrier of the present embodiment method is 0.75g/cm
3, in solution, density is about 1.23g/cm
3, under 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%, than adding bio-carrier, approximately do not improved 27%; Its total nitrogen (TN) clearance surpasses 53%, than adding bio-carrier, has not approximately improved 31%.
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. a porous light charcoal base bio-carrier, it is characterized in that: it is to be that coke powder/polyvinyl alcohol gel mixture that crosslinking reaction obtains foaming occurs raw material at normal temperatures 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, the weight ratio of polyvinyl alcohol water solution and cross-linking agent solution is 20～50: 1, and its preparation method comprises the following steps successively:
1) by the water-soluble weight percentage that is configured to of polyvinyl alcohol, be first, 5～15% polyvinyl alcohol water solution;
2), secondly getting coke powder, to put into weight percent concentration be that 10～50% salpeter solution carries out oxidation modification processing, processes after 2～5h coke powder washing to neutral;
3), then coke powder is carried out to drying treatment;
4) cross-linking agent solution that the whipping agent that is, 0.2～2% by dried coke powder, weight percent concentration again, weight percent concentration are 0.5～1.5% adds in described polyvinyl alcohol water solution, stir 2～5h, obtain coke powder/polyvinyl alcohol gel mixture of foaming; 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 and obtains coke powder/polyvinyl alcohol gel film after processing through knifing, curtain coating;
6), then coke powder/polyvinyl alcohol gel film is carried out to heat modification processing, described heat modification treatment process is to be placed in the baking oven of 80～150 ℃ to toast 1～2h;
7), finally coke powder/polyvinyl alcohol gel film is cooled to room temperature, carry out as required stripping and slicing, granulation, obtain porous light carbon back microbe carrier.
2. porous light charcoal base bio-carrier according to claim 1, is characterized in that: 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.
3. a preparation method for porous light charcoal base bio-carrier described in claim 1, is characterized in that: this preparation method comprises the following steps successively:
1) by the water-soluble weight percentage that is configured to of polyvinyl alcohol, be first, 5～15% polyvinyl alcohol water solution;
2), secondly getting coke powder, to put into weight percent concentration be that 10～50% salpeter solution carries out oxidation modification processing, processes after 2～5h coke powder washing to neutral;
3), then coke powder is carried out to drying treatment;
4) cross-linking agent solution that the whipping agent that is, 0.2～2% by dried coke powder, weight percent concentration again, weight percent concentration are 0.5～1.5% adds in described polyvinyl alcohol water solution, stir 2～5h, obtain coke powder/polyvinyl alcohol gel mixture of foaming; 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 and obtains coke powder/polyvinyl alcohol gel film after processing through knifing, curtain coating;
6), then coke powder/polyvinyl alcohol gel film is carried out to heat modification processing, described heat modification treatment process is to be placed in the baking oven of 80～150 ℃ to toast 1～2h;
7), finally coke powder/polyvinyl alcohol gel film is cooled to room temperature, carry out as required stripping and slicing, granulation, obtain porous light carbon back microbe carrier.
4. the preparation method of porous light charcoal base bio-carrier according to claim 3, is characterized in that: the polymerization degree of polyvinyl alcohol described in step 1) is greater than 1750.
5. according to the preparation method of porous light charcoal base bio-carrier described in claim 3 or 4, it is characterized in that: step 2) described in coke powder granularity be 180～300 orders.
6. according to the preparation method of porous light charcoal base bio-carrier described in claim 3 or 4, 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. according to the preparation method of porous light charcoal base bio-carrier described in claim 3 or 4, it is characterized in that: the linking agent described in step 4) is a kind of in glutaraldehyde, formaldehyde or oxalic dialdehyde.
8. according to the preparation method of porous light charcoal base bio-carrier described in claim 3 or 4, 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, is characterized in that: the whipping agent described in step 4) is sodium lauryl sulphate or polyoxyethylenated alcohol sodium sulfate.
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| CN103408097B (en) * | 2013-08-27 | 2015-06-10 | 武汉钢铁(集团)公司 | Method for removing sulfides in coking wastewater |
| CN104628123B (en) * | 2015-01-28 | 2016-06-01 | 苏州赛华仪控股份有限公司 | A kind of modification biological slag microbe carrier and its preparation method |
| 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 |
| 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 |
| 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 |
| 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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| CN1152958C (en) * | 1995-10-04 | 2004-06-09 | 索罗蒂亚公司 | Porous polymeric biosupports and their use in biotreatment of aqueous waste streams |
| JP3722696B2 (en) * | 1998-03-31 | 2005-11-30 | サムソンエンジニアリングコーポレーションリミテッド | Wastewater treatment method for removal of organic matter and nitrogen |
| CN1114729C (en) * | 2000-07-21 | 2003-07-16 | 中国科学院山西煤炭化学研究所 | Preparation method of foam block active carbon fibre |
| CN1269743C (en) * | 2003-11-03 | 2006-08-16 | 中国科学院成都生物研究所 | Carrier for waste water biological treatment and its preparation |
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Effective date of registration: 20170717 Address after: 430083, Hubei Wuhan Qingshan District Factory No. 2 Gate joint stock company organs Patentee after: Wuhan iron and Steel Company Limited Address before: 430080 Hubei, Wuhan, Wuchang Friendship Road, No. 999, block A, floor 15 Patentee before: Wuhan Iron & Steel (Group) Corp. |