CN100359009C - Preparation of chitosan imbedded microbe sphere and method for biological treatment of sewage using same - Google Patents
Preparation of chitosan imbedded microbe sphere and method for biological treatment of sewage using same Download PDFInfo
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- CN100359009C CN100359009C CNB2004100862993A CN200410086299A CN100359009C CN 100359009 C CN100359009 C CN 100359009C CN B2004100862993 A CNB2004100862993 A CN B2004100862993A CN 200410086299 A CN200410086299 A CN 200410086299A CN 100359009 C CN100359009 C CN 100359009C
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- chitosan
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- spheroid
- sphere
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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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention discloses a method for preparing a chitosan imbedded microbe sphere and carrying out the biological treatment of sewage by using the sphere. The method for preparing the sphere comprises the following steps: firstly, a chitosan is made into solution; pH value is controlled within the range of 4.5 to 8.5, and the range is suitable for a microbe to live; the solution reacts with solidified liquid; microbes for treating different kinds of sewage are added to the prepared chitosan solution by a biologic embedded method so that the hollow imbedded microbe sphere with multiple functions is prepared. The sphere is applied to the treatment of domestic sewage or special industrial sewage. The quantity of the treated sewage is great, the quality of the effluent water of the domestic sewage reaches the effluent index of the primary standard of China, and the quality of the effluent water of the industrial sewage reaches more than 90%.
Description
Technical field
The present invention relates to a kind of biochemical basis that utilizes and make microbe carrier, and be applied to and carry out biological treatment of sewage to the preparation of the chitosan imbedded microbe spheroid of sewage disposal and with spheroid in the processing of sanitary sewage or extraordinary sewage.
Background technology
Chitosan is white or white translucent pressed powder, and is nontoxic, tasteless, and acid and alkali-resistance is corrosion-resistant, high temperature resistant, anti-daylight, and performance is very stable.On chemical classification, belong to glycosaminoglycan.As a kind of natural high moleculer eompound, has sucting wet air permeability, degradable, chitosan with natural organic vesicular structure has very strong crystallized ability to microorganism, and to the harmless nontoxic good avidity that has of microorganism, these material nature reserves are abundant to be that the nature reserves are only second to cellulosic second largest natural reproducible resource.Because chitosan unique texture characteristics and abundant natural reserves, since the eighties in biochemical field with it as the carrier of immobilized cell and enzyme Application and Development in addition.
Summary of the invention
The purpose of this invention is to provide a kind of characteristic of utilizing chitosan to have, adopt chitosan imbedded microbe to be used for sewage is handled.
Technical scheme of the present invention is: earlier chitosan is made solution, its pH value is controlled at the pervasive scope of microorganism, react with solid solution again, utilize biological entrapping method with different action characteristics, the microorganism that can handle dissimilar sewage adds the chitosan solution that has disposed and makes the multi-functional spheroid of the hollow of imbedded microbe sanitary sewage and industrial special sewage are handled.Chitosan spheroid of the present invention adopts entrapping method (interface freezing method) to prepare, and has certain elastic hollow sphere structure, this spheroid is nontoxic and good biocompatibility is arranged to enzyme and microorganism, can make microbe carrier and use on sewage treatment project.
The preparation method of a kind of chitosan imbedded microbe spheroid of the present invention comprises the following steps:
(a) system solvent:
Acetate is dissolved in makes dilute solution of acetic acid in the pure water, concentration proportioning 1ml: 100ml, stand-by;
(b) system solid solution:
Trisodium phosphate is dissolved in becomes solution in the pure water, concentration proportioning 2g: 100ml;
Potassium oxalate is dissolved in becomes solution in the pure water, concentration proportioning 4g: 100ml;
With sodium pyrophosphate solution and Potassium Oxalate Solution is that 1: 1 volume ratio is mixed, and its pH=8～10 are stand-by;
(c) system chitosan solution:
Chitosan is added in (a) solution, and concentration proportioning 2g: 100ml constantly stirs simultaneously, and stir about 20～30 minutes is stand-by;
(d) system chitosan microorganism mixed solution:
Desired microorganisms is joined in (c) solution, consumption is no more than 1/5～2/5 of liquor capacity, and pH=4.5～8.5 are stand-by;
(e) spheroid of system chitosan imbedded microbe:
With balling-up equipment (d) drips of solution is added in (b) solution, after the balling-up, solidify 10～15min in (b) solution, the solid solution of putting into again after the dilution (b) continues curing 30～40min, and the ratio of its water and solid solution (b) is 2: 1.
The preparation method of described chitosan imbedded microbe spheroid, its microorganism is aerobic microbiological or anaerobic sludge; Wherein, add thalline in the microorganism and adsorb heavy metal element, its thalline is rhizopus, yeast saccharomyces cerevisiae, flavus, Aspergillus, marine alga.
Can be used as for the spherical particles that carries out after the sewage disposal:
(1), because the microorganism of the inner embedding of spheroid is disposed the organic matter degradation of spherome surface, the spheroid with sufficient mechanical strength that filter can be selected continues to use through the washing back.
(2), for the spheroid of fragmentation, utilize the resistance against diseases and the degradability of chitosan, it is used for compost, the dead microorganism of spheroid inside also can play the effect of Natural fertilizers simultaneously, is a kind of excellent organic fertilizer, can be made for thing and absorb.
Advantage of the present invention: chitosan nature reserves are abundant, and ball making method is simple and easy to do, and batch process speed is fast, and spherome surface is coarse, and porosity is big, helps the carry microorganism; The microbial load height, treatment capacity is big, and no excess sludge is discharged, and has inner embedding anaerobism of spheroid and the aerobic dual processing effect of outside biofilm concurrently.Sewage enters second pond, and some lose the effect accelerate precipitation that the damaged particle of chitosan that effect is scattered also can play flocculation agent.
Description of drawings
Fig. 1 is the schema that the present invention prepares the chitosan spheroid.
Fig. 2 is the electron microscope photo scanning of chitosan spheroid.
Fig. 3 is the synoptic diagram of waste disposal plant.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of preparation method of chitosan imbedded microbe spheroid, the technology of its preparation chitosan spheroid as shown in Figure 1, it comprises the following steps:
(a) system solvent:
Acetate is dissolved in makes dilute solution of acetic acid in the pure water, concentration proportioning 1ml: 100ml, stand-by;
(b) system solid solution:
Trisodium phosphate is dissolved in becomes solution in the pure water, concentration proportioning 2g: 100ml;
Potassium oxalate is dissolved in becomes solution in the pure water, concentration proportioning 4g: 100ml;
With sodium pyrophosphate solution and Potassium Oxalate Solution is that 1: 1 volume ratio is mixed, and its pH=8～10 are stand-by;
(c) system chitosan solution:
Chitosan is added in (a) solution, and concentration proportioning 2g: 100ml constantly stirs simultaneously, and stir about 20～30 minutes is stand-by;
(d) system chitosan microorganism mixed solution:
Desired microorganisms is joined in (c) solution, consumption is no more than 1/5～2/5 of liquor capacity, and pH=4.5～8.5 are stand-by;
(e) spheroid of system chitosan imbedded microbe:
With balling-up equipment (d) drips of solution is added in (b) solution, after the balling-up, solidify 10～15min in (b) solution, the solid solution of putting into again after the dilution (b) continues curing 30～40min, and the ratio of its water and solid solution (b) is 2: 1; The optics electron-microscope scanning picture of the chitosan spheroid that makes is seen shown in Figure 2.
The present invention carries out biological treatment of sewage with the chitosan imbedded microbe spheroid, is that the spheroid of the chitosan imbedded microbe that will prepare through above-mentioned (e) joins in the sewage biodegrade and handles, and its consumption is no more than reaction tank volumetrical 1/3.
Embodiment 1
High density artificial sewage to the preparation of 1000ml laboratory handles:
Experimental installation: use novel LINPOR-C device, structure as shown in Figure 3.The LINPOR-C device is made up of reaction tank, second pond, mud passage and entery and delivery port, when carrying out sewage disposal, the chitosan imbedded microbe spheroid for preparing is joined in the reaction tank, utilize the adsorptive power absorb polluted matter of chitosan, utilize the microorganism of inner embedding that organic pollutent biodegrade that waits is handled again; Water after the chitosan powder that is scattered is managed everywhere flows in the second pond together, and utilizes the flocculence of chitosan to help treating water in the second pond sedimentation, has promptly played the effect of flocculation agent.
Instrument: the agent of NQT-79 rotary viscosity, PH meter.
Article: chitosan (food grade, deacetylation 98%), Glacial acetic acid, trisodium phosphate (analytical pure), potassium oxalate (analytical pure), microorganism (active sludge),
Artificial preparation sewage (COD=1000mg/l):
Peptone 60g, extractum carnis 40g, NaCl 1g,
KCl 1.4g、 CaCl
2 1.4g、 MgSO
4 1g、
FeCl
31g mix to add in the 1L distilled water, and is mixing low-grade fever and stir evenly.
Formulations prepared from solutions:
(a) preparation solvent: the 1g Glacial acetic acid is dissolved in to make concentration in the 100ml pure water be 1% dilute solution of acetic acid, stand-by;
(b) preparation solid solution:
The 2g trisodium phosphate is dissolved in to make concentration in the 100ml pure water be 2% sodium pyrophosphate solution;
The 4g potassium oxalate is dissolved in to make concentration in the 100ml pure water be 4% Potassium Oxalate Solution;
Be that 1: 1 volume ratio is mixed into 190～200ml solid solution with sodium pyrophosphate solution and Potassium Oxalate Solution again, its pH=9, stand-by;
(c) preparation chitosan solution:
The 2g chitosan is joined in 100ml (a) solution, constantly stir simultaneously, stir about 20 minutes, stand-by;
(d) preparation chitosan microorganism mixed solution:
The microorganism of 20～40ml volume is joined in (c) solution, pH=5, stand-by;
(e) preparation chitosan imbedded microbe spheroid:
With needle tubing (d) drips of solution is added in (b) solution, obtain the hollow ball of inner embedding concentrate microbial, and in (b) solution, solidify 10～15min, (b) solution for continuous of putting into again after the dilution is solidified about 30～40min, its concentration is 30～40% of former solid solution, just can make the chitosan hollow ball of 130～150ml volume.This chitosan hollow ball has certain toughness, elasticity.
(f) sewage disposal:
To join among the high density artificial sewage of 1000ml laboratory preparation biodegrade through the chitosan spheroid that (e) prepares 130～150ml volume handles.
Experimentation:
The high density artificial sewage of 1000ml laboratory preparation is put in the reaction tank of LINPOR-C device, the chitosan hollow ball is joined in the reaction tank again, aeration time 8h, the water after the processing send into second pond and carry out water outlet behind the flocculation sediment.
Before the processing: COD=1000mg/l BOD=200mg/l;
Handle the back: COD=65mg/l, clearance: 93.5%; BOD=28mg/l, clearance: 86%.
Embodiment 2
With the porous spheroid of the chitosan imbedded active sludge municipal effluent of carrying out a biological disposal upon in self-control sbr reactor device, each result is shown in table 3.1.
The chitosan imbedded active sludge porous of table 3.1 spheroid biological treatment municipal effluent effluent index
| COD value (mg/l) | BOD value (mg/l) | The pH value | |
| Former water goes out water removal rate | 165.13 53.31 67.7％ | 45 18 60.0％ | 7.37 8.05 |
The conclusion (in the pH value is 7.00～8.50, and the chitosan dosage is 1: 3 with the ratio of the amount of disposing of sewage, and aeration is cultivated 3d) that chitosan imbedded active sludge porous spheroid biological treatment artificial sewage is obtained is applied to Treating Municipal Sewage, has obtained obvious effects.The COD value of water outlet is 53.31mg/l,＜60mg/l; The BOD value is 18mg/l,＜30mg/l; The pH value is 8.05, and within 6.00～9.00 scope, each index has all reached national grade one discharge standard, sees Table 3.1.Water outlet after the processing is as clear as crystal, and turbidity is very low.The bead of not cracked chitosan imbedded active sludge is dissectd out,, find that microbial survival is good at the microscopically microscopy.Experimental results show that, the method that chitosan imbedded active sludge porous spheroid is carried out a biological disposal upon to sewage, not only can handle the sewage of high density, the municipal effluent lower to concentration, the good treatment effect is also arranged, each index of water outlet all can reach national grade one discharge standard, is a kind of extraordinary biological sewage treatment novel method.This method is simple to operate, treatment effect good, possesses the feasibility that is applied to put into practice, and wide application prospect is arranged.
Embodiment 3
Dyeing waste water is handled
Device is with embodiment 1.
Dual mode is mainly passed through in the application of chitosan in dyeing and printing sewage is handled: the one, chitosan is made particle or powder directly is used for dyeing and printing sewage and handles as adhesive flocculant, as in the waste water of continuous flow (dye strength is 0.05%) make sorbent material with chitosan; The 2nd, with chitin modified or crosslinked, be used further to absorbing dye.
In the present invention,, select first method for use, relation by marriage red (a kind of matching stain) is carried out adsorption test with particulate state chitosan (interior do not load microorganism) according to the preparation-obtained carrier granule ball of contriver characteristics.
Treatment time: 6h
Result: its clearance is 75%, is equivalent to 1kg chitosan absorption 45g dyestuff.
Concrete data compare:
| Chitosan | Chitin | Mierocrystalline cellulose | |
| Adsorptive capacity (m mol/g) | 17 | 2.1 | 1.0 |
Compare with Mierocrystalline cellulose, chitosan to the adsorptive power of dyestuff greater than Mierocrystalline cellulose.Simultaneously, chitosan all has certain adsorptivity to matching stain, reactive dyestuffs, mordant dye, substantive dyestuff.And the dye molecule with acidic-group is shown excellent adsorptive power, adsorptive capacity is cellulosic tens times, is the several times of granular carbon.
Embodiment 4
Industrial Wastewater Treatment
Absorption to heavy metal ion
Utilize the sequestering action of chitosan, absorption property is handled the water body of heavy metal contamination, is to administer the effective ways that pollute.Chitosan is by amino, hydroxyl and heavy metal ion Mn in the molecule
+(Mn
+=Hg
2+, Cd
2+Deng) effect formation stable chelate.Chitosan can adsorb or capture inorganic metal ion, can effectively capture organic mercury again.Not only adsorb face width, and the adsorptive capacity height.See the following form:
Chitosan is to the absorption of metal ion
| Metal ion | Hg 2+ | Zn 2+ | Cd 2+ | Ni 2+ | Cu 2+ | Ag + | Fe 2+ | pd 2+ |
| Adsorptive capacity (m mol/g) | 5.6 | 3.70 | 2.78 | 3.15 | 3.12 | 3.25 | 5.48 | 4.52 |
Chitosan is to the order of heavy metal ion adsorbed ability: Hg
2+＞Pd
2+＞Zn
2+＞Cd
2+Simultaneously can also embedding have adsorbing thalline to make adsorption effect better to heavy metal ion:
Different thalline are to the absorption of heavy metal
| The thalline title | Species of metal ion |
| Rhizopus yeast saccharomyces cerevisiae flavus, Aspergillus marine alga | Cd + Cu 2+ Zn 2+ Hg 2+ Cd 2+ Cu 2+ Zn 2+ pb 2+ Cd 2+ Cr 2+ |
Claims (2)
1, a kind of preparation method of chitosan imbedded microbe spheroid comprises the following steps:
(a) system solvent:
Acetate is dissolved in makes dilute solution of acetic acid in the pure water, concentration proportioning 1ml: 100ml, stand-by;
(b) system solid solution:
Trisodium phosphate is dissolved in becomes solution in the pure water, concentration proportioning 2g: 100ml;
Potassium oxalate is dissolved in becomes solution in the pure water, concentration proportioning 4g: 100ml;
With sodium pyrophosphate solution and Potassium Oxalate Solution is that 1: 1 volume ratio is mixed, and its pH=8～10 are stand-by;
(c) system chitosan solution:
Chitosan is added in (a) solution, and concentration proportioning 2g: 100ml constantly stirs simultaneously, and stir about 20～30 minutes is stand-by;
(d) system chitosan microorganism mixed solution:
Desired microorganisms is joined in (c) solution, consumption is no more than 1/5～2/5 of liquor capacity, and pH=4.5～8.5 are stand-by;
(e) spheroid of system chitosan imbedded microbe:
With balling-up equipment (d) drips of solution is added in (b) solution, after the balling-up, solidify 10～15min in (b) solution, the solid solution of putting into again after the dilution (b) continues curing 30～40min, and the ratio of its water and solid solution (b) is 2: 1.
2, the preparation method of chitosan imbedded microbe spheroid according to claim 1 is characterized in that: described microorganism is an active sludge, and described active sludge is aerobic activated sludge or anaerobic sludge; Wherein, add thalline in the active sludge and adsorb heavy metal element, its thalline is rhizopus, yeast saccharomyces cerevisiae, flavus, Aspergillus, marine alga.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384761C (en) * | 2005-05-23 | 2008-04-30 | 南京工业大学 | Method and apparatus for immobilizing cells to treat wastewater |
| CN101570366B (en) * | 2009-06-12 | 2012-05-30 | 北京金源化学集团有限公司 | Compound liquid for enhancing sewage biological treatment |
| CN101940912B (en) * | 2010-09-27 | 2012-05-09 | 浙江农林大学 | Method for producing adsorbent by coupling chitosan and bamboo charcoal with sodium alginate |
| CN103725620A (en) * | 2014-01-03 | 2014-04-16 | 湖南大学 | Activated sludge yeast for treating high-concentration decentralized domestic sewage as well as preparation method and application of activated sludge yeast |
| CN106745689B (en) * | 2017-02-15 | 2020-11-13 | 山东泽辉新材料股份有限公司 | Biological rotating disc treatment method for synthetic leather wastewater |
| CN106904709A (en) * | 2017-03-27 | 2017-06-30 | 山东钢铁集团日照有限公司 | A kind of method for preparing hollow ball flocculant |
| CN108545839A (en) * | 2018-06-28 | 2018-09-18 | 新乡市逸凡蔚岚堆肥生物技术有限公司 | A kind of biomass generator |
| CN109261086B (en) * | 2018-09-07 | 2021-06-29 | 中国水产科学研究院南海水产研究所 | Active microcapsule and preparation method and application thereof |
| CN110255722A (en) * | 2019-07-31 | 2019-09-20 | 淮北市菲美得环保科技有限公司 | A kind of dyeing waste water treatment based on immobilized microorganisms agent and preparation method thereof |
| CN111875066A (en) * | 2020-07-31 | 2020-11-03 | 浙江双良商达环保有限公司 | Immobilized microorganism particles for degrading grease in kitchen wastewater, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
Non-Patent Citations (2)
| Title |
|---|
| 固定化微生物技术及其在废水处理中的应用. 刘蕾等.甘肃科技，第20卷第3期. 2004 * |
| 微生物固定化的发展及在废水处理中的应用. 王里奥等.重庆大学学报，第27卷第3期. 2004 * |
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