CN101045921A - Microbe immobilicing gel material for waste water treatment - Google Patents

Microbe immobilicing gel material for waste water treatment Download PDF

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Publication number
CN101045921A
CN101045921A CNA2007100675628A CN200710067562A CN101045921A CN 101045921 A CN101045921 A CN 101045921A CN A2007100675628 A CNA2007100675628 A CN A2007100675628A CN 200710067562 A CN200710067562 A CN 200710067562A CN 101045921 A CN101045921 A CN 101045921A
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microbe
chitosan
gel material
water treatment
waste water
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CN100506985C (en
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李济吾
蔡伟建
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological 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

The present invention discloses one kind of microbe immobilizing gel material for waste water treatment. The microbe immobilizing gel material consists of chitosan, bentonite, CMC, glytaraldehyde, etc. and its preparation process includes the following steps: drying and grinding bentonite, adding bentonite powder into CMC solution, mixing with acetic acid solution of chitosan in certain concentrate to produce cross-linking reaction and to obtain the gel material comprising chitosan, bentonite and CMC and named as CBC. The microbe immobilizing gel material has certain mechanical strength, low cost, moderate water absorption, no degradation by microbe in water, high heat stability, high acid and base resisting stability, high adsorbing and mass transfer performance, long service life, no harm to microbe and wide application foreground in microbe immobilizing water treatment.

Description

A kind of microbe immobilicing gel material for waste water treatment
Technical field
The present invention relates to a kind of microbe immobilicing gel material for waste water treatment.
Background technology
Immobilized microorganism technique is meant by the method for chemistry or physics free cell or microorganism fixed, and makes it to become water insoluble but still has a technology of high biological activity fixed growth body.It is to develop the seventies in 20th century to form on the enzyme immobilization technology basis, and the later stage seventies, wastewater treatment new technology was efficiently developed in an urgent demand, so begin immobilized microorganism technique is introduced field of waste water treatment owing to water pollution problems is serious day by day.This technology can be fixed the dominant bacteria or the microorganism that filter out, thereby constitute a Waste Water Treatment efficiently, compare with traditional suspended biological facture and to have the processing efficiency height, stability is strong, sludge output is few, no sludge bulking, good effect of separating solid from liquid, advantages such as the device volume is little demonstrate wide application prospect in wastewater treatment.But, at present owing to do not have economy, efficient, durable immobilization material, immobilized microorganism wastewater processing technology also to be in laboratory study and small-scale application experimental stage.Exploitation screening ideal microbe immobilizing material is that can immobilized microorganism technique drop into practical key.
Immobilization material commonly used mainly contains inorganic materials (sintered glass, gac, silicon bath soil, porous ceramics etc.) and organic materials (polyose, protein, hollow fiber etc.).Inorganic immobilization material is more cheap as prices such as pottery, nut-shell, alginatess, but fixed effect is poor, and microorganism easily comes off; Organic materials such as urethane, polyvinyl alcohol organic polymer good fixing effect such as (PVA), but the microorganism growth activity is low, and bioaffinity is poor, and costs an arm and a leg, and the degradation effect of pollutent is undesirable.The further immobilization material carrier of development of new excellent property, all most important to the development of the treatment effect that improves immobilization technology and use properties and immobilization technology.
Bentonitic reserves are big, and are cheap, have good adsorption performance and ion-exchange performance, are widely used in field of waste water treatment.Chitosan is a kind of natural water treatment flocculant, takes off the chitosan that forms behind the hexanoyl and has a large amount of amino and hydroxyl, add carboxyl methyl cellulose after, utilize the carboxyl in the CMC molecule and the NH of chitosan-acetic acid solution 3 +The ion exchange reaction of group, obtain the polyamphoteric electrolyte mixture, add wilkinite simultaneously, make unnecessary chitosan be adsorbed on the surface of bentonitic main component montmorillonite, add a certain amount of glutaraldehyde spirituous solution, two aldehyde radicals of glutaraldehyde molecule can be respectively with carrier and aglucon on amino form schiff bases, their forms with five carbon bridges are coupled together, make its further crosslinked sclerosis, finally form the gel material of holey.This material be a kind of inorganic-organic plural gel body, price is low, good hydrophilic property, bioaffinity is good, microorganism is easily fixing and not by its decomposition, stable performance, the life-span is long, has very big actual application value and wide application prospect.
Summary of the invention
The purpose of this invention is to provide a kind of microbe immobilicing gel material for waste water treatment.
Microbe immobilicing gel material for waste water treatment is made up of chitosan, wilkinite, Xylo-Mucine and glutaraldehyde, wilkinite and carboxymethylcellulose sodium solution mass ratio are 1: 1~1: 10, glutaraldehyde spirituous solution and chitosan solution volume ratio are 30: 1~100: 1, and the mass ratio of wilkinite and chitosan is 10: 1~40: 1.
Described wilkinite particle diameter is 8 orders~180 orders, and wilkinite is calcium-base bentonite or sodium bentonite.
Described penta 2 dialdehyde spirituous solutions are the industrial spirit solution of glutaraldehyde mass concentration 0.1%~5%.
Described chitosan-acetic acid solution is the acetum of chitosan mass concentration 0.3%~10%;
The density range of described material is 1.00~1.17 * 10 3Kgm -3, the water-intake rate scope is 12.00~18.50, better heat stability.
Advantage of the present invention:
(1) microbial immobilized CBC gelatinous material is cheap.It is to utilize chitosan and wilkinite and CMC to make by certain proportioning crosslinking reaction to form, and main component is a wilkinite, and low price is for commercial application provides condition.
(2) density of microbial immobilized CBC gelatinous material is more slightly bigger than water, can not be compacted in water and influences thalli growth on it.
(3) Heat stability is good of microbial immobilized CBC gelatinous material, heat resisting temperature is wide.
(4) ph stability of immobilization CBC gelatinous material is good, and the pH of waste water swelling behavior influence to the CBC material in 3.5~11 scopes is little, can not destroy.
(5) mass transfer and the stability influence of the CBC material of salt ionic concentration are less, and after aqueous solution intermediate ion concentration (NaCl concentration) surpassed 0.4%, the mass-transfer performance of immobilization CBC gelatinous material no longer changed along with the increase of concentration.
(6) the CBC gelatinous material has good mass-transfer performance, absorption property and bioaffinity.Chitosan energy and wilkinite, three kinds of materials of CMC and glutaraldehyde all react, and have the effect of bridge in whole material.Bentonitic interpolation can increase the settling property of material, and can provide certain inorganic salt minerals matter for microorganism growth, and the interpolation of CMC helps improve the swelling behavior of material, material is further hardened, the mechanical property of strongthener.
Embodiment
The microbial immobilized CBC gelatinous material of use in waste water treatment is made up of chitosan, wilkinite, Xylo-Mucine (CMC) and glutaraldehyde, and the density range of CBC material is 1.00~1.17 * 10 3Kgm -3, the water-intake rate scope is 12.00~18.50, in wider temperature range (10~90 ℃), and the better heat stability of this material, pH swelling behavior influence to the CBC material in 3~11 scopes is little.Effects of ion concentration (NaCl concentration) has very big influence to the mass-transfer performance of CBC material, and after NaCl concentration surpassed 0.4%, mass-transfer performance no longer changed along with the increase of concentration.The CBC material has excellent mass transferring performance, can see through larger molecular organics matter such as tropeolin-D, and tropeolin-D is by outer during toward internal diffusion, mass transfer coefficient K 1=0.0040~0.0055mmmin -1, tropeolin-D by interior when the external diffusion, K 2=0.01~0.016mmmin -1
Embodiment 1
Select for use 8~40 purpose wilkinite mixings in 20mL CMC solution, place, the 0.5g chitosan is dissolved in the 25mL acetum, mix wilkinite-CMC solution and chitosan-acetum, high-speed stirring 20min under 400rpm, add and add water after the 30mL glutaraldehyde solution is fixed 1 hour and cut into needed size, be dipped in the water, place standby after 1 day.
The density of the CBC material of preparation is 1.06 * 10 3Kgm -3, water absorbent rate is 16.50, better heat stability in 10~90 ℃ of temperature ranges, and pH is ph stability in 3~10 scopes.After NaCl concentration surpassed 0.4%, mass-transfer performance no longer changed along with the increase of concentration.The CBC material has excellent mass transferring performance, and tropeolin-D is by outer during toward internal diffusion, mass transfer coefficient K 1=0.0046mmmin -1, tropeolin-D by interior when the external diffusion, K 2=0.016mmmin -1
Get weight in wet base 20gCBC material in 50mL200mgL -1In the phenol solution, add 1mL sickle-like bacteria spore suspension, at 30 ℃, under the 100rpm, cultivate one section after 4 days, recording the phenol clearance is 97.30%.The CBC gelatinous material is placed in solution and is not all occurred more than 1 year decomposing and the biological degradation phenomenon stable in properties.
Embodiment 2
Select for use the above wilkinite mixing of 180 orders in 20mL CMC solution, place, the 0.75g chitosan is dissolved in the 25mL acetum, mix wilkinite-CMC solution and chitosan-acetum, high-speed stirring 20min under 400rpm, add and add water after the 30mL glutaraldehyde solution is fixed 4 hours and cut into needed size, be dipped in the water, place standby after 1 day.
The density of the CBC material of preparation is 1.17 * 10 3Kgm -3, water absorbent rate is 17.50, better heat stability in 10~80 ℃ of temperature ranges, and pH is ph stability in 3~10 scopes.After NaCl concentration surpassed 0.5%, mass-transfer performance no longer changed along with the increase of concentration.The CBC material has excellent mass transferring performance, and tropeolin-D is by outer during toward internal diffusion, mass transfer coefficient K 1=0.0052mmmin -1, tropeolin-D by interior when the external diffusion, K 2=0.012mmmin -1
Get weight in wet base 20gCBC material in 50mL250mgL -1In the phenol solution, add 1mL sickle-like bacteria spore suspension, at 30 ℃, under the 100rpm, cultivate one section after 4 days, recording the phenol clearance is 92.30%.The CBC gelatinous material is placed in solution and is not all occurred more than 1 year decomposing and the biological degradation phenomenon stable in properties.
Embodiment 3
Select for use 40-180 purpose wilkinite mixing in 20mL CMC solution, place, the 1.0g chitosan is dissolved in the 25mL acetum, mix wilkinite-CMC solution and chitosan-acetum, high-speed stirring 20min under 400rpm, add and add water after the 30mL glutaraldehyde solution is fixed 2 hours and cut into needed size, be dipped in the water, place standby after 1 day.
The density of the CBC material of preparation is 1.09 * 10 3Kgm -3, water absorbent rate is 18.50, better heat stability in 10~80 ℃ of temperature ranges, and pH is ph stability in 3~10 scopes.After NaCl concentration surpassed 0.4%, mass-transfer performance no longer changed along with the increase of concentration.The CBC material has excellent mass transferring performance, and tropeolin-D is by outer during toward internal diffusion, mass transfer coefficient K 1=0.0055mmmin -1, tropeolin-D by interior when the external diffusion, K 2=0.013mmmin -1
Get weight in wet base 20gCBC material in 50mL100mgL -1In the neutral blue dye solution, add 1mL sickle-like bacteria spore suspension, at 30 ℃, under the 100rpm, cultivate one section after 4 days, recording neutral blue dyestuff clearance is 98.30%.The CBC gelatinous material is placed in solution and is not all occurred more than 1 year decomposing and the biological degradation phenomenon stable in properties.
Embodiment 4
Select for use the above wilkinite mixing of 180 orders in 40mL CMC solution, place, the 0.5g chitosan is dissolved in the 25mL acetum, mix wilkinite-CMC solution and chitosan-acetum, high-speed stirring 20min under 400rpm, add and add water after the 40mL glutaraldehyde solution is fixed 2 hours and cut into needed size, be dipped in the water, place standby after 1 day.
The density of the CBC material of preparation is 1.11 * 10 3Kgm -3, water absorbent rate is 15.50, better heat stability in 10~80 ℃ of temperature ranges, and pH is ph stability in 3~10 scopes.After NaCl concentration surpassed 0.4%, mass-transfer performance no longer changed along with the increase of concentration.The CBC material has excellent mass transferring performance, and tropeolin-D is by outer during toward internal diffusion, mass transfer coefficient K 1=0.0045mmmin -1, tropeolin-D by interior when the external diffusion, K 2=0.014mmmin -1
Get weight in wet base 20gCBC material in 50mL100mgL -1In the acid blue dye solution, add 1mL sickle-like bacteria spore suspension, at 30 ℃, under the 100rpm, cultivate one section after 4 days, recording the acid blue dye clearance is 99.20%.The CBC gelatinous material is placed in solution and is not all occurred more than 1 year decomposing and the biological degradation phenomenon stable in properties.

Claims (5)

1. microbe immobilicing gel material for waste water treatment, it is characterized in that forming by chitosan, wilkinite, Xylo-Mucine and glutaraldehyde, wilkinite and carboxymethylcellulose sodium solution mass ratio are 1: 1~1: 10, glutaraldehyde spirituous solution and chitosan-acetic acid solution volume ratio are 30: 1~100: 1, and the mass ratio of wilkinite and chitosan is 10: 1~40: 1.
2. a kind of microbe immobilicing gel material for waste water treatment according to claim 1 is characterized in that described wilkinite particle diameter is 8 orders~180 orders, and wilkinite is calcium-base bentonite or the swelling of sodium base.
3. a kind of microbe immobilicing gel material for waste water treatment according to claim 1 is characterized in that the industrial spirit solution that described glutaraldehyde spirituous solution is a glutaraldehyde mass concentration 0.1%~5%.
4. a kind of microbe immobilicing gel material for waste water treatment according to claim 1 is characterized in that described chitosan-acetic acid solution is the acetum of chitosan mass concentration 0.3%~10%.
5. a kind of microbe immobilicing gel material for waste water treatment according to claim 1, the density range that it is characterized in that described material is 1.00~1.17 * 10 3Kgm -3, the water-intake rate scope is 12.00~18.50.
CNB2007100675628A 2007-03-15 2007-03-15 Microbe immobilicing gel material for waste water treatment Expired - Fee Related CN100506985C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104894099A (en) * 2015-06-12 2015-09-09 福建省农业科学院中心实验室 Bacteria immobilization particles for water purification and preparation method of bacteria immobilization particles
CN106186352A (en) * 2016-07-25 2016-12-07 江苏星鑫分离设备制造有限公司 A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water
CN108114694A (en) * 2017-11-30 2018-06-05 广西大学 A kind of organic decoration magnetism alkaline calcium bentonite and preparation method thereof
CN108579693A (en) * 2018-05-23 2018-09-28 东华理工大学 A kind of preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aeroge
CN117343924A (en) * 2023-12-01 2024-01-05 中建易通科技股份有限公司 Composite biological microbial agent for water quality improvement and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104894099A (en) * 2015-06-12 2015-09-09 福建省农业科学院中心实验室 Bacteria immobilization particles for water purification and preparation method of bacteria immobilization particles
CN106186352A (en) * 2016-07-25 2016-12-07 江苏星鑫分离设备制造有限公司 A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water
CN108114694A (en) * 2017-11-30 2018-06-05 广西大学 A kind of organic decoration magnetism alkaline calcium bentonite and preparation method thereof
CN108114694B (en) * 2017-11-30 2020-12-25 广西大学 Organic modified magnetic alkaline calcium bentonite and preparation method thereof
CN108579693A (en) * 2018-05-23 2018-09-28 东华理工大学 A kind of preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aeroge
CN108579693B (en) * 2018-05-23 2021-01-05 东华理工大学 Preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aerogel
CN117343924A (en) * 2023-12-01 2024-01-05 中建易通科技股份有限公司 Composite biological microbial agent for water quality improvement and preparation method thereof
CN117343924B (en) * 2023-12-01 2024-03-22 五康生物科技股份有限公司 Composite biological microbial agent for water quality improvement and preparation method thereof

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