CN1868919A - Suspension microorganism carrier and its preparation method - Google Patents
Suspension microorganism carrier and its preparation method Download PDFInfo
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- CN1868919A CN1868919A CNA2006100517460A CN200610051746A CN1868919A CN 1868919 A CN1868919 A CN 1868919A CN A2006100517460 A CNA2006100517460 A CN A2006100517460A CN 200610051746 A CN200610051746 A CN 200610051746A CN 1868919 A CN1868919 A CN 1868919A
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- polyvinyl alcohol
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
A suspended microbe carrier with high microbial affinity, adsorption and hydrophilicity is a macroreticular skeleton and millipore skeleton combined structure. Its preparing process includes such steps as preparing the aqueous solution of polyvinyl alcohol, proportionally adding sulfuric acid and formaldehyde solution, reaction, adding powdered imorganic filler, high-speed stirring, filling it in a mould, foaming by filling the pre-heated air via millipore air distributor, and treating at 40-80 deg.C for 4-24 hr.
Description
Technical field
The invention belongs to environmental engineering material field, relate to a kind of porous microbial carrier preparation methods.
Background technology
(aeration tank) introduces the high-effective microorganism solid support material in traditional sewage biochemical processing device, for improve wastewater treatment ability and efficient, the reduction surplus sludge volume is significant.At present, the material of using during wastewater biochemical is handled mainly is the hard-wired suspension type fibrous bundle of employing, but it remains in installation and change trouble, the limited deficiency that waits of load microbial biomass.
Because the macroporous polymer carrier has the space that very high Gong microorganism grows surely, its research and development has important use and is worth.Announced a kind of sponge microorganism particle carrier of porous polyethylene alcohol formal among the CN1216581A, its aperture is 20-300 μ m.Because lack macroporous structure, the absorption of nutrition and metabolite and the passage of discharge are limited, also are unfavorable for the quick transmission of material in gas, liquid and the solid phase.Disclosing a kind of high water absorption polyvinyl alcohol foam among the CN1557872A, is the continuous hole-opening foaming body that 2000～3200 full-bodied polyvinyl formal post-foaming obtains by the polymerization degree, 8.6～32 times of suction multiples, unit weight 30～105Kg/m3.Owing to take chemical foaming agent sodium bicarbonate etc., it is difficult to accurate control punch distribution and structure, and the material that obtains is unordered random pore structure.In addition, the normal pore former starchy material that adds in the manufacturing processed of polyvinylalcohol sponge or foam owing to need the back to clean to remove the operation of its residue, has increased difficulty and the labour intensity produced, and its manufacturing process awaits improving.
Though polyvinyl alcohol material is hydrophilic, it has good bioaffinity, be very suitable for as microbial carrier material, but because present polyvinylalcohol sponge or foam are subjected to the restriction of its density and pore structure, its manufactured materials raw materials cost is higher, with the low price and the high performance requirement of filler distance is arranged still from Industrial Wastewater Treatment, its application is restricted.
Summary of the invention
The object of the present invention is to provide inorganic/polyvinyl alcohol composite foam material microbe carrier of use in waste water treatment and preparation method thereof.Described solid support material is used for wastewater treatment, has the macropore and the micropore unitized construction of rule, and specific surface area is big, and absorption property is good, has physical strength preferably, and is with low cost.Described preparation method is simple, and the structure of material and performance are easy to control.
The present invention is realized by following technical proposals: the inorganic/polyvinyl alcohol composite foam material microbe carrier that is used for wastewater treatment, this carrier microorganisms carrier is the black elastomer particles, the structure that it is characterized in that it is netted macropore and porous skeleton unitized construction, mesh aperture is between 0.5～2mm, the skeleton micropore size is less than 100 μ m, and unit weight is 10～30Kg/m
3, specific surface area is at 20～100m
2Between/the g.
The preparation method of mentioned microorganism carrier is characterized in that may further comprise the steps:
(1) with 100 parts of polyvinyl alcohol polyvinyl alcohol water solution of making 8～12% (Wt%) soluble in water;
(2) sulfuric acid and 30～200 parts of formalins of 50～180 part 40% are successively joined in the polyvinyl alcohol water solution, under 20～60 ℃ of temperature, reacted 5～20 minutes; Add 5～50 parts of Powdered mineral fillers then, under the high-speed stirring it is uniformly dispersed;
(3) above-mentioned mixed liquor is injected acidproof mould,, feed the preheated air foaming, make material liquid volume increase to original 2～10 times by the micropore gas distributor;
(4) sealed mold chamber was handled 4～24 hours under 40～80 ℃ of temperature;
(5) open mould, take out forming composition, water cleans up, and is cut into finished product.
Powdered mineral filler of the present invention is the vesicular thing with absorption property, as gac, diatomite and sepiolite etc., or is their mixture, and its particle diameter is preferably less than 50 μ m.
What the present invention adopted is micropore gas distribution foaming mode, promptly by the micropore gas distributor air is presorted to be made into uniform small bubbles and to foam.Gas distributor of the present invention can be micropore glass, micropore ceramics or microcellular polymeric material etc., and its micropore size is preferably in 10～100 mu m ranges.
The present invention has following characteristics:
(1) inorganic/polyvinyl alcohol composite foam material microbial carrier material is open netted macroscopic void and porous skeleton unitized construction, can give full play to its space multistory effect as microbial carrier material.The macroscopic void space structure helps high loading load microorganism, and helping provides passage smoothly for the absorption and the discharge of nutrition and metabolite, helps the transmission of material in gas, liquid and the solid phase; And the coarse microvoid structure of skeleton can be given its high-specific surface area, helps increasing speed, fastness and the quantity of microorganism colonization simultaneously.
(2) inorganic filler components that adds in the manufacturing processed can play complex effects such as reinforcement, adjusting microvoid structure, raising absorption property.
(3) take micropore gas distribution foaming can control the porosity of polyvinyl alcohol foam body, bubble pore size and distribution thereof effectively.The unit weight of PVA-based porous material can be reduced to less than 30Kg/m by this method
3Below, be significantly less than the unit weight level of this type of material at present, make it make raw materials cost and reduce greatly, accord with the low-cost requirement of water treatment field large-scale industrial application.
Of the present invention inorganic/the polyvinyl alcohol composite foam material microbial carrier material integrates the big surface of micropore, macropore permeability, wetting ability and strong adsorptivity, have that mass-transfer performance is good, microorganism excellent affinity, biological charge capacity height, physics and distinguishing features such as chemical stability is good, suspension flowability and low cost of manufacture, can satisfy the application requiring of water treatment fully with floating stuffing.
Description of drawings
The stereoscan photograph of the inorganic/PVA foamed composite of the macroporous netlike open-celled structure that Fig. 1 prepares for the embodiment of the invention 1.
Fig. 2 is the stereoscan photograph of the inorganic/PVA foamed composite of the macroporous netlike open-celled structure prepared for the embodiment of the invention 2
Fig. 3 is the stereoscan photograph of the inorganic/PVA foamed composite of the macroporous netlike open-celled structure prepared for the embodiment of the invention 3
Embodiment
The present invention will be further described by following examples.
Embodiment 1:
With the 100g polymerization degree is that 1799 polyvinyl alcohol under agitation joins in the 750ml water, progressively is warming up to 90 ℃, to the polyvinyl alcohol dissolving fully.
When treating that the polyvinyl alcohol solution temperature is reduced to 50 ℃, slowly add the sulfuric acid of 180ml 40%, this moment, system temperature can rise, and when treating that temperature falls back to 50 ℃, added the 100ml formalin and carried out acetalation.After 10 minutes, add 15g sepiolite powder, stir fast it is uniformly dispersed in mutually at solution.Then, mixing of materials liquid is poured in the acidproof mould of plastics, fed preheated air by mold bottom, make its volume increase to 5000ml, stop ventilation, die sealing is placed under 50 ℃ of temperature handled 6 hours by the micropore glass gas distributor.Open mould at last, take out the grey foam, the sulfuric acid that the water flush away is residual cuts into the cubic granules of 10～30mm size.
The massfraction of dry back sample load sepiolite is 13%.The stereoscan photograph accompanying drawing 1 of material shows that the gained material is opening rule mesh pore structure, and its pore structure is similar to reticulated polyurethane foam, and the aperture is between 0.5～2mm, and its skeleton micropore size is less than 10 μ m.Unit weight is about 23Kg/m
3, specific surface area is 22m
2/ g.
Embodiment 2:
With the 100g polymerization degree is that 1799 polyvinyl alcohol under agitation joins in the 900ml water, progressively is warming up to 90 ℃, to the polyvinyl alcohol dissolving fully.
When treating that the polyvinyl alcohol solution temperature is reduced to 30 ℃, slowly add the sulfuric acid of 160ml 40%, this moment, system temperature can rise, and when treating that temperature falls back to 30 ℃, added the 80ml formalin and carried out acetalation.After 15 minutes, add the 20g Powdered Activated Carbon, stir fast it is uniformly dispersed in mutually at solution.Then, mixing of materials liquid is poured in the acidproof mould of plastics, fed preheated air by mold bottom, make its volume increase to 7600ml, stop ventilation, die sealing is placed under 40 ℃ of temperature handled 20 hours by the micropore glass gas distributor.Open mould at last, take out the black foam of moulding, the sulfuric acid that the water flush away is residual cuts into the cubic granules of 10～30mm size.
The foam load type active carbon massfraction that obtains is 17%, its outward appearance and mesh-structured consistent with embodiment 1, and the aperture is between 0.5～2mm, and unit weight is about 15Kg/m
3
The stereoscan photograph of material sees that Fig. 2 shows, its skeleton micropore size than embodiment 1 gained sample more greatly, most of below 30 μ m, its hole is more flourishing, specific surface area is 34m
2/ g.
Embodiment 3:
Press the same method of embodiment 2, the addition of gac changes 40g into, and other composition and working method are constant.The foam load type active carbon massfraction that obtains is 28%, and its outward appearance and pore structure are consistent with embodiment 2, and the aperture is between 0.5～2mm, and unit weight is about 18Kg/m
3
The stereoscan photograph of material sees that Fig. 3 can show, its skeleton micropore size than embodiment 2 gained samples more greatly, most of below 60 μ m, its hole is more flourishing, specific surface area is 69m
2/ g.
Embodiment 4:
Press in the synthetic glass post of embodiment 2 gained sample 6L input 20L capacity, topped up with water is ventilated by the bottom.In 1 to 30 day cycle, when ventilation intensity was high, the solid support material fluidisation produced more violent collision phenomenon between the particle in water in aeration; When stopping to ventilate, solid support material suction back is because proportion is slightly larger than the value of water, and it is deposited on container bottom, the shape of material does not have any change, and water is the complete transparent stillness of night, the good stability of illustrative material, the fragment that can not come off under crash situation, usage safety performance is good.
Add inoculation of activated-sludge afterwards and substratum is cultivated, change once fresh substratum and water source every day.Cultivate after 7 days, under the condition of little aeration, carrier along the turbulence of air flow line circulation, is complete fluidized state in post, be covered with faint yellow microorganism on the three-dimensional space of carrier, and water is a clear liquid, and microorganism implantation, growth in the carrier duct easily is described.Stop ventilation, the load microbe carrier all sinks to the synthetic glass column bottom.
The result shows, its microorganism excellent affinity of porous carrier materials of the present invention, biofilm are fast, and Stability Analysis of Structures is indeformable, good, the anti-biological degradation of chemical stability, and it is mobile good to suspend behind the load microorganism, is suitable for the performance requriements of water treatment with floating stuffing.
Claims (6)
1, a kind of suspension microorganism carrier, carrier is inorganic/polyvinyl alcohol composite foam material, is the black elastomer particles, it is characterized in that structure is netted macropore and porous skeleton unitized construction, mesh aperture is between 0.5～2mm, and the skeleton micropore size is less than 100 μ m, and unit weight is 10～30Kg/m
3, specific surface area is at 20～100m
2Between/the g.
2, the preparation method of carrier according to claim 1 is characterized in that:
(1) with 100 parts of polyvinyl alcohol polyvinyl alcohol water solution of making 8～12% (Wt%) soluble in water;
(2) sulfuric acid and 30～200 parts of formalins of 50～180 part 40% are successively joined in the polyvinyl alcohol water solution, under 20～60 ℃ of temperature, reacted 5～20 minutes; Add 5～50 parts of Powdered mineral fillers then, under the high-speed stirring it is uniformly dispersed;
(3) above-mentioned mixed liquor is injected acidproof mould,, feed the preheated air foaming, make material liquid volume increase to original 2～10 times by the micropore gas distributor;
(4) sealed mold chamber was handled 4～24 hours under 40～80 ℃ of temperature;
(5) open mould, take out forming composition, water cleans up, and is cut into finished product.
3, the preparation method of carrier according to claim 2 is characterized in that described mineral filler is gac, diatomite and sepiolite or their mixture.
4,, it is characterized in that described mineral filler particle diameter is less than 50 μ m according to the preparation method of claim 2,3 described carriers.
5, the preparation method of carrier according to claim 2 is characterized in that described micropore gas distributor is micropore glass, micropore ceramics or microcellular polymeric material.
6,, it is characterized in that described micropore gas distributor aperture 10～100 μ m according to the preparation method of claim 1,2 described carriers.
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|---|---|---|---|
| CNA2006100517460A CN1868919A (en) | 2006-05-29 | 2006-05-29 | Suspension microorganism carrier and its preparation method |
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|---|---|---|---|
| CNA2006100517460A CN1868919A (en) | 2006-05-29 | 2006-05-29 | Suspension microorganism carrier and its preparation method |
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|---|---|---|---|---|
| CN101428901B (en) * | 2008-12-09 | 2011-01-26 | 沈阳师范大学 | Bamboo charcoal-polyvinyl formal biological carrier and preparation thereof |
| CN101691436B (en) * | 2009-10-13 | 2012-01-11 | 四川环能德美科技股份有限公司 | Magnetic microbial carrier and preparation method thereof |
| CN101422669B (en) * | 2008-11-26 | 2012-02-08 | 南昌大学 | Preparation method of hydrophilicity macromolecule micropore filter material |
| CN103159330A (en) * | 2013-04-07 | 2013-06-19 | 武汉钢铁(集团)公司 | Porous light-weight carbon-based biological carrier and preparation method thereof |
| CN103224283A (en) * | 2013-05-15 | 2013-07-31 | 上海立源水处理技术有限责任公司 | Honeycomb modified biological stuffing applied to water treatment and preparation method thereof |
| CN103253776A (en) * | 2013-05-28 | 2013-08-21 | 武汉钢铁(集团)公司 | Semi-coke microbial carrier and preparation method thereof |
| CN103342412A (en) * | 2013-08-02 | 2013-10-09 | 武汉钢铁(集团)公司 | Coke particle biomembrane carrier and preparation method thereof |
| CN103351062A (en) * | 2013-07-08 | 2013-10-16 | 华侨大学 | Magnetic microbial carrier and preparation method thereof |
| CN103524648A (en) * | 2013-08-28 | 2014-01-22 | 华侨大学 | Foaming polyvinyl formal microbial carrier and preparation method thereof |
| CN103951044A (en) * | 2014-05-23 | 2014-07-30 | 哈尔滨理工大学 | Novel non-sintered biological stuffing rapid in biofilm formation and preparation method thereof |
| CN104176833A (en) * | 2013-07-08 | 2014-12-03 | 华侨大学 | Preparation method of magnetic microbial carrier |
| CN105779426A (en) * | 2016-04-28 | 2016-07-20 | 广州甘蔗糖业研究所 | Porous immobilized yeast and preparation method and application thereof |
| CN106186284A (en) * | 2016-08-26 | 2016-12-07 | 李勇锋 | Microbe carrier |
| CN106495306A (en) * | 2016-11-17 | 2017-03-15 | 南京悠谷知识产权服务有限公司 | A kind of environmental protection material for water treatment and preparation method thereof |
| CN107649493A (en) * | 2017-10-31 | 2018-02-02 | 上海恒晔生物科技有限公司 | A kind of preparation method and waste disposal method of the bio-matrix for loading strain |
| CN108373549A (en) * | 2018-01-24 | 2018-08-07 | 鹤山市怡欣纤维制品有限公司 | The production technology of latex foam |
| WO2022163262A1 (en) * | 2021-01-29 | 2022-08-04 | 株式会社クラレ | Hydrogel porous molded product and method for producing same, microorganism carrier, and water treatment method |
| CN115197515A (en) * | 2022-09-16 | 2022-10-18 | 中煤科工集团杭州研究院有限公司 | Biological fluidized carrier material and preparation method and application thereof |
| CN115418066A (en) * | 2022-10-14 | 2022-12-02 | 中煤科工集团杭州研究院有限公司 | Biological carrier material for sewage treatment and preparation method thereof |
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2006
- 2006-05-29 CN CNA2006100517460A patent/CN1868919A/en active Pending
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| CN101422669B (en) * | 2008-11-26 | 2012-02-08 | 南昌大学 | Preparation method of hydrophilicity macromolecule micropore filter material |
| CN101428901B (en) * | 2008-12-09 | 2011-01-26 | 沈阳师范大学 | Bamboo charcoal-polyvinyl formal biological carrier and preparation thereof |
| CN101691436B (en) * | 2009-10-13 | 2012-01-11 | 四川环能德美科技股份有限公司 | Magnetic microbial carrier and preparation method thereof |
| CN103159330A (en) * | 2013-04-07 | 2013-06-19 | 武汉钢铁(集团)公司 | Porous light-weight carbon-based biological carrier and preparation method thereof |
| CN103224283A (en) * | 2013-05-15 | 2013-07-31 | 上海立源水处理技术有限责任公司 | Honeycomb modified biological stuffing applied to water treatment and preparation method thereof |
| CN103253776A (en) * | 2013-05-28 | 2013-08-21 | 武汉钢铁(集团)公司 | Semi-coke microbial carrier and preparation method thereof |
| CN103253776B (en) * | 2013-05-28 | 2014-11-12 | 武汉钢铁(集团)公司 | Semi-coke microbial carrier and preparation method thereof |
| CN103351062B (en) * | 2013-07-08 | 2014-11-12 | 华侨大学 | Magnetic microbial carrier |
| CN103351062A (en) * | 2013-07-08 | 2013-10-16 | 华侨大学 | Magnetic microbial carrier and preparation method thereof |
| CN104176833B (en) * | 2013-07-08 | 2016-08-24 | 华侨大学 | A kind of preparation method of magnetic microbial carrier |
| CN104176833A (en) * | 2013-07-08 | 2014-12-03 | 华侨大学 | Preparation method of magnetic microbial carrier |
| CN103342412A (en) * | 2013-08-02 | 2013-10-09 | 武汉钢铁(集团)公司 | Coke particle biomembrane carrier and preparation method thereof |
| CN103524648A (en) * | 2013-08-28 | 2014-01-22 | 华侨大学 | Foaming polyvinyl formal microbial carrier and preparation method thereof |
| CN103951044B (en) * | 2014-05-23 | 2016-01-06 | 哈尔滨理工大学 | A kind of non-sintered rapid biofilm biologic packing material and preparation method thereof |
| CN103951044A (en) * | 2014-05-23 | 2014-07-30 | 哈尔滨理工大学 | Novel non-sintered biological stuffing rapid in biofilm formation and preparation method thereof |
| CN105779426B (en) * | 2016-04-28 | 2019-01-18 | 广东省生物工程研究所（广州甘蔗糖业研究所） | A kind of porous fixed yeast and the preparation method and application thereof |
| CN105779426A (en) * | 2016-04-28 | 2016-07-20 | 广州甘蔗糖业研究所 | Porous immobilized yeast and preparation method and application thereof |
| CN106186284B (en) * | 2016-08-26 | 2020-06-23 | 李勇锋 | Microbial carrier |
| CN106186284A (en) * | 2016-08-26 | 2016-12-07 | 李勇锋 | Microbe carrier |
| CN106495306A (en) * | 2016-11-17 | 2017-03-15 | 南京悠谷知识产权服务有限公司 | A kind of environmental protection material for water treatment and preparation method thereof |
| CN107649493A (en) * | 2017-10-31 | 2018-02-02 | 上海恒晔生物科技有限公司 | A kind of preparation method and waste disposal method of the bio-matrix for loading strain |
| CN108373549A (en) * | 2018-01-24 | 2018-08-07 | 鹤山市怡欣纤维制品有限公司 | The production technology of latex foam |
| WO2022163262A1 (en) * | 2021-01-29 | 2022-08-04 | 株式会社クラレ | Hydrogel porous molded product and method for producing same, microorganism carrier, and water treatment method |
| CN115197515A (en) * | 2022-09-16 | 2022-10-18 | 中煤科工集团杭州研究院有限公司 | Biological fluidized carrier material and preparation method and application thereof |
| CN115197515B (en) * | 2022-09-16 | 2022-12-09 | 中煤科工集团杭州研究院有限公司 | Biological fluidized carrier material and preparation method and application thereof |
| CN115418066A (en) * | 2022-10-14 | 2022-12-02 | 中煤科工集团杭州研究院有限公司 | Biological carrier material for sewage treatment and preparation method thereof |
| CN115418066B (en) * | 2022-10-14 | 2024-04-19 | 中煤科工集团杭州研究院有限公司 | Biological carrier material for sewage treatment and preparation method thereof |
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Open date: 20061129 |