CN1269743C - Carrier for waste water biological treatment and its preparation - Google Patents
Carrier for waste water biological treatment and its preparation Download PDFInfo
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- CN1269743C CN1269743C CNB2003101108424A CN200310110842A CN1269743C CN 1269743 C CN1269743 C CN 1269743C CN B2003101108424 A CNB2003101108424 A CN B2003101108424A CN 200310110842 A CN200310110842 A CN 200310110842A CN 1269743 C CN1269743 C CN 1269743C
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- Prior art keywords
- carrier
- pva
- wastewater treatment
- powder
- biological wastewater
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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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- Biological Treatment Of Waste Water (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The present invention relates to an organism vector. In order to solve the problems of easy breaking, large mass transfer resistance, gas generation and upward floating, etc. of the existing vector particles, the present invention discloses a vector used for the biological wastewater treatment and a preparation method thereof. The vector of the present invention is prepared by the steps of mixing of PVA and ingredients, freezing primary shaping, pre-crosslink by using formaldehyde crosslink liquid, drying, pulverization, sieving, crosslink, water washing and drying. The vector of the present invention has the advantages of easy molding, good microbial fixing performance, convenient preparation and operation, etc.
Description
One, technical field:
The present invention relates to a kind of bio-carrier, be specifically related to a kind of microbial fixed carrier that is applied to biological wastewater treatment.
Two, background technology:
The key of treatment based on immobilized microorganisms organic waste water is to select suitable microbe carrier.PVA is a kind of polymer embedded material that Japanese scholar at first develops, owing to characteristics such as nontoxic, antimicrobial decomposition, physical strength be high and inexpensive come into one's own.Result of study shows that the surviving rate of bacterium is all satisfactory with the efficient of handling waste water.But defectives such as it exists, and embedded particles is easily broken, resistance to mass transfer is big, aerogenesis come-up and loss of activity.The polyvinyl alcohol hydrogel that existing most research is adopted utilizes cold method (perhaps adding calcium chloride in refrigerating process) preparation.The moulding mechanism of cold method hydrogel is that the polyvinyl alcohol physical crystal in the freeze-thaw process forms cross-linking set, and then forms network structure.Because the crystallization of the polyvinyl alcohol hydrogel granule interior that cold method makes is perfect inadequately, thereby in process of the test, cause producing in the aeration tank of wastewater treatment a large amount of foams, this not only makes the COD numerical value for the treatment of water increase, and can reduce greatly the work-ing life of hydrogel.In addition, though it is less to contain the hydrogel polyvinyl alcohol stripping of calcium chloride, in use, calcium ion can form throw out with some the negatively charged ion liberation in the waste water inevitably, thereby has reduced processing efficiency.
So now mainly there is following problem in the microbe carrier that uses: defectives such as embedded particles is easily broken, resistance to mass transfer is big, aerogenesis come-up and loss of activity; Adopt at present mostly boric acid to make linking agent, but exist, cause lower and PVA of immobilized microorganism activity and acid reaction slow, problems such as PVA gel balling-up difficulty as crosslinked fluid pH4; Because the crystallization of the polyvinyl alcohol hydrogel granule interior that cold method makes is perfect inadequately, thereby in process of the test, cause handling in the aeration tank of waste water and produce a large amount of foams, this not only makes the COD numerical value of treat effluent increase, and the work-ing life of hydrogel can reduce greatly, in addition, though it is less to contain the hydrogel polyvinyl alcohol stripping of calcium chloride, in use, calcium ion can form throw out with some negatively charged ion in the waste water inevitably, thereby has reduced processing efficiency; Use PVA gel sets microorganism generally to adopt entrapping method at present: PVA heating back is water-soluble, gelation takes place add additive in its aqueous solution after, or (10 ℃) freezing formation gel at low temperatures, thereby the microorganism embedding is fixed in the gel network, but a large amount of preparation of industrialization technology of immobilized cell can't satisfy large-scale application on engineering at present.
Three, summary of the invention:
At above problem, the invention discloses the carrier that is used for biological wastewater treatment that a kind of PVA of employing and batch mixes, freezing initial shaping, the precrosslink of formaldehyde crosslinking liquid, drying, pulverizing, screening, crosslinked, washing and drying means make.
The invention also discloses the preparation method of the carrier that is used for biological wastewater treatment: with PVA and batching sodium alginate, reduced iron powder, CaCO
30.3%, SiO
2The mixed PVA hydrogel solution that gets of powder, can regulate the proportion of carrier as required, according to required particle diameter, adopt cold method that material is finalized the design for the first time with mould, adopt formaldehyde crosslinking liquid to carry out precrosslink at temperature 25-30 ℃ then, natural air drying or oven drying at low temperature below 60 ℃, with pulverizer carrier in blocks is pulverized again, sub-elect the product of required particle diameter with screen cloth, once more 25-30 ℃ and formaldehyde crosslinking liquid crosslinking reaction, reaction back water flush away crosslinked fluid obtains wet carrier, but also natural air drying or oven drying at low temperature below 60 ℃ make dried carrier.Carrier is generally the small-particle of oyster white and light red brown.
Carrier can adopt the absorption method fixation of microbe among the present invention, makes microorganic adhesion on carrier as carrier and microorganism being mixed together cultivate, and carrier can form microbial film in 3-5 days, and carrier fixation of microbe flora is abundant, and the absorption biomass is big.
Above-mentioned food ingredient and consumption: sodium alginate 1～5%, reduced iron powder 2%, CaCO
30.3%, SiO
2Powder 4%; Formaldehyde crosslinking liquid: formaldehyde 25g/L, Na
2SO
4150g/L, sulfuric acid 200g/L
Making PVA hydrogel solution method is: take by weighing quantitative PVA solid with tap water washing 2 to 3 times, soaked overnight is made into 8% PVA solution; Heating in water bath maintains the temperature at more than 95 ℃, does not stop to be stirred to PVA and dissolves fully, loses the regimen condition as discovery in the heat-processed and adds moisture content immediately, carefully pours the sodium alginate, reduced iron powder, the CaCO that have prepared in advance again into
3And SiO
2Powder, limit bevelling stir, and prevent the powder not molten thing that conglobulates, and continue to stir, and mix in hydrogel until the batching that adds.
The suitableeest dry density of this carrier is 0.6281g/cm
3, wet density is 1.0757g/cm
3, density is 1.0-1.5g/cm behind the fixation of microbe
3, expansion rate of water absorption is 246.15%; Settling property is good, and subsidence rate is 0.0159m/s.
Bio-carrier of the present invention has the following advantages:
1. the PVA particulate vector easy-formation of this prepared is gone back may command particle grain size and proportion; PVA is difficult for stripping; Can fix abundant microorganism species by absorption, not need embedding in advance, solve the problem that large-scale industrialization prepares the embedded immobilization gel.This carrier is easy to fluidisation, makes the abundant contact reacts of microbial film and matrix, improves degradation efficiency, cuts down the consumption of energy simultaneously.
2. the fixation of microbe performance is good: through sem test, this carrier can be fixed abundant microorganism species, forms microbial film.
3. imbedded microbe in advance can directly adopt absorption method to carry out immobilization, is adapted at using in the scale operation treatment unit.
Four, embodiment
Embodiment 1
At first produce the PVA hydrogel solution, the composition of PVA hydrogel solution: PVA 8%, sodium alginate 1%, reduced iron powder 2%, CaCO
30.3%, SiO
2Powder 4%; Formaldehyde crosslinking liquid: formaldehyde 25g/L, NaSO4150g/L, sulfuric acid 200g/L
Making method: take by weighing quantitative PVA solid with tap water washing 2 to 3 times according to aforementioned proportion earlier, soak and spend the night, be made into 8% PVA solution; Heating in water bath maintains the temperature at more than 95 ℃ again, does not stop to be stirred to PVA and dissolves fully, loses the regimen condition as discovery in the heat-processed and adds moisture content immediately; Carefully pour the sodium alginate, reduced iron powder, the CaCO that have prepared in advance again into
3And SiO
2Powder, limit bevelling stir, and prevent the powder not molten thing that conglobulates.Continue to stir, in hydrogel, mix until the batching that adds; Preparing shaper then, decide according to the carrier particle diameter of required preparation, is example with the carrier for preparing particle diameter 0.5-1.0mm particle diameter, and mould is a rectangle, and length and width can be made by oneself, but highly are the big or small 1mm of particle diameter.Polyethylene (PE) film is spread in inside; The PVA hydrogel solution that dissolving is good is poured in the mould while hot, smears evenly, presses with die cover plate; The mould that presses is put into freezing plant, more than-4 ℃ of freezing 24h.Take out mould after freezing the finishing, put into the tap water immersion and thaw, open mould after thawing, take out gel-film, put into formaldehyde crosslinking liquid and descended crosslinked 0.5 hour for 30 ℃.Take out the gel-film after crosslinked, with the clear water rinsing for several times, be placed on dry airy place and spread nature out and dry, if not crisp firmly after drying in the air, could be 60 ℃ of oven dry a few hours down; Carrier after stiff is fully pulverized with pulverizer, sieved, select the carrier granule of 0.15～1.0mm, the carrier granule of selecting is crosslinked more than 1 hour down at 30 ℃ with formaldehyde crosslinking liquid, with the clear water rinsing for several times, promptly obtain wet carrier after finishing, put into container at last and preserve.If dry a few hours down at 60 ℃, promptly get dried carrier.
Embodiment 2
The composition of PVA hydrogel solution: PVA solution: PVA 8%, sodium alginate 2%, reduced iron powder 2%, CaCO
30.3%, SiO
2Powder 4%; Formaldehyde crosslinking liquid: formaldehyde 25g/L, NaSO4 150g/L, sulfuric acid 200g/L
Making method: take by weighing quantitative PVA solid with tap water washing 2 to 3 times according to aforementioned proportion, soaked overnight is made into 8% PVA solution; Heating in water bath maintains the temperature at more than 95 ℃, does not stop to be stirred to PVA and dissolves fully, loses the regimen condition as discovery in the heat-processed and adds moisture content immediately, carefully pours the sodium alginate, reduced iron powder, the CaCO that have prepared in advance again into
3And SiO
2Powder, limit bevelling stir, and prevent the powder not molten thing that conglobulates, and continue to stir, and mix in hydrogel until the batching that adds; Preparing shaper, decide according to the carrier particle diameter of required preparation, is example with the carrier for preparing particle diameter 0.5-1.0mm particle diameter, and mould is a rectangle, and length and width can be made by oneself, but highly are the big or small 1mm of particle diameter.Polyethylene (PE) film can be spread in inside.The PVA hydrogel solution that dissolving is good is poured in the mould while hot, smears evenly, presses with die cover plate again; The mould that presses is put into freezing plant, more than-4 ℃ of freezing 24h; Take out mould after freezing the finishing, put into the tap water immersion and thaw.Open mould after thawing, take out gel-film, put into formaldehyde crosslinking liquid and descended crosslinked 1 hour for 25 ℃; Take out the gel-film after crosslinked, with the clear water rinsing for several times, be placed on dry airy place and spread nature out and dry (about 25 ℃ of room temperature); Carrier after stiff is fully pulverized with pulverizer, sieved, select the carrier granule of 0.15～1.0mm; The carrier granule of selecting is crosslinked more than 1 hour under 25 ℃ with formaldehyde crosslinking liquid, with the clear water rinsing for several times, promptly obtain wet carrier after finishing, put into container at last and preserve.If dry a few hours down at 60 ℃, promptly get dried carrier.
Embodiment 3
In useful volume is in the aerobic internal circulation fluidized bed reactor of 15L, carrier and microorganism are mixed together cultivation, matrix is the water outlet of glucose water distribution after anaerobic biological treatment, COD1500-2000mg/L, flooding quantity 30L/d, the reactor organic loading is 3-6gCOD/dL, water outlet COD100-150mg/L after the wastewater treatment, and the COD clearance can reach 90-95%.Carrier can form microbial film in 3-5 days, through scanning electron microscopic observation, carrier fixation of microbe flora is abundant, and this carrier absorption biomass can reach 0.204g/cm
3
Claims (5)
1, a kind of carrier that is used for biological wastewater treatment is characterized in that: this carrier adopts PVA8% and batching sodium alginate 1～5%, reduced iron powder 2%, CaCO
30.3%, SiO
2Powder 4% is mixed into the PVA hydrogel solution, adopts mould that this hydrogel solution is carried out freezing initial shaping, then with the precrosslink of formaldehyde crosslinking liquid, makes through super-dry, pulverizing, screening, crosslinked, washing and drying means again, and its suitableeest dry density is 0.6281g/cm
3, wet density is 1.0757g/cm
3, density is 1.0～1.5g/cm behind the fixation of microbe
3, expansion rate of water absorption is 246.15%, subsidence rate is 0.0159m/s.
2, the described carrier that is used for biological wastewater treatment of claim 1, its preparation method is: with PVA and batching sodium alginate, reduced iron powder, CaCO3, the mixed PVA hydrogel solution that gets of SiO2 powder, regulate the proportion of carrier as required, according to required particle diameter, adopt cold method that material is finalized the design for the first time with mould, adopt formaldehyde crosslinking liquid to carry out precrosslink at temperature 25-30 ℃ then, natural air drying or oven drying at low temperature below 60 ℃, with pulverizer carrier in blocks is pulverized again, sub-elect the product of required particle diameter with screen cloth, once more 25-30 ℃ and formaldehyde crosslinking liquid crosslinking reaction, reaction back water flush away crosslinked fluid, obtain wet carrier, natural air drying or oven drying at low temperature below 60 ℃ make dried carrier.
3, the carrier that is used for biological wastewater treatment according to claim 1 and 2, it is characterized in that: the composition of described formaldehyde crosslinking liquid is: formaldehyde 25g/L, Na
2SO
4150g/L, sulfuric acid 200g/L.
4, the carrier that is used for biological wastewater treatment according to claim 1 and 2 is characterized in that: make PVA hydrogel solution method and wash 2 to 3 times with tap water for taking by weighing quantitative PVA solid, soaked overnight is made into 8% PVA solution; Heating in water bath, maintain the temperature at more than 95 ℃, not stopping to be stirred to PVA dissolves fully, lose the regimen condition as discovery in the heat-processed and add moisture content immediately, pour the sodium alginate, reduced iron powder, CaCO3 and the SiO2 powder that have prepared in advance again into, the limit bevelling stirs, and prevents the powder not molten thing that conglobulates, continue to stir, in hydrogel, mix until the batching that adds.
5, claim 1 or the 2 described carriers that are used for biological wastewater treatment are mixed together cultivation with microorganism, make microorganic adhesion on carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101108424A CN1269743C (en) | 2003-11-03 | 2003-11-03 | Carrier for waste water biological treatment and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101108424A CN1269743C (en) | 2003-11-03 | 2003-11-03 | Carrier for waste water biological treatment and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1613798A CN1613798A (en) | 2005-05-11 |
| CN1269743C true CN1269743C (en) | 2006-08-16 |
Family
ID=34759247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101108424A Expired - Fee Related CN1269743C (en) | 2003-11-03 | 2003-11-03 | Carrier for waste water biological treatment and its preparation |
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| Country | Link |
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| CN (1) | CN1269743C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101479200B (en) * | 2006-07-06 | 2012-06-13 | 株式会社日立工业设备技术 | Entrapping immobilization pellets, wastewater treatment system using the entrapping immobilization pellets and wastewater treatment method |
| 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 |
| JP2013544643A (en) * | 2010-10-26 | 2013-12-19 | ノボザイムス バイオロジカルズ，インコーポレイティド | Wastewater treatment composition |
| CN102173493A (en) * | 2011-03-08 | 2011-09-07 | 北京市环境保护科学研究院 | Process for removing polyvinyl alcohol in waste water |
| CN102776169A (en) * | 2012-08-13 | 2012-11-14 | 广西宏业环保节能工程有限公司 | Immobilized competent cell vector with biological catalysis element and preparation method of immobilized competent cell vector |
| CN103159330B (en) * | 2013-04-07 | 2014-03-12 | 武汉钢铁(集团)公司 | Porous light-weight carbon-based biological carrier and preparation method thereof |
| CN103789296A (en) * | 2014-01-13 | 2014-05-14 | 华东理工大学 | Immobilized microorganism spherule for repairing field and preparation method thereof |
| CN108002547B (en) * | 2017-12-13 | 2021-03-02 | 西安建筑科技大学 | Coal chemical industry wastewater advanced treatment method based on living cell immobilization technology |
-
2003
- 2003-11-03 CN CNB2003101108424A patent/CN1269743C/en not_active Expired - Fee Related
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|---|---|
| CN1613798A (en) | 2005-05-11 |
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