CN104498469A - Preparation method of polyurethane foam immobilized microbe for treatment of azo dye sewage - Google Patents
Preparation method of polyurethane foam immobilized microbe for treatment of azo dye sewage Download PDFInfo
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- CN104498469A CN104498469A CN201410751556.4A CN201410751556A CN104498469A CN 104498469 A CN104498469 A CN 104498469A CN 201410751556 A CN201410751556 A CN 201410751556A CN 104498469 A CN104498469 A CN 104498469A
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- polyurethane foam
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- immobilized microorganism
- azoic dyestuff
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Abstract
The invention relates to a preparation method of a polyurethane foam immobilized microbe for treatment of azo dye sewage. The preparation method comprises the following steps: performing ultrasonic dispersion on polyester polyol, triethanolamine, water, methyl silicone oil, dibutyltin dilaurate and graphite felt powder after grinding together, then adding diphenylmethane diisocyanate (MDI), stirring until whitening, rapidly transferring, naturally foaming to obtain polyurethane foam, washing with distilled water for several times, then drying, preparing a lysogeny broth (LB) culture medium, putting the polyurethane foam into the LB culture medium, sterilizing together, cooling, then inoculating an immobilized microbe, namely a Stenotrophomonas maltophilia strain T-8, performing shaking culture and washing with the distilled water for several times for preparation. The polyurethane foam with the immobilized microbe prepared by the preparation method provided by the invention has a macroporous reticular structure, high specific surface area and hydroxyl and other groups, and can effectively immobilize the microbe and greatly improve the effect of decoloring azo dye.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of polyurethane foam immobilized microorganism preparation method processing azoic dyestuff sewage.
Background technology
In recent years, increasingly strict due to environmental protection standard and policy, azo dye wastewater due to its quantum of output large, difficult treatment, causes the attention of people day by day.Immobilized cell technology is owing to can maintain the cell concentration of greater density, Black Liquor with Efficient Bacteria is kept to live, have the ability that stronger resistance to toxic substance impacts, be widely used in azo dye wastewater process, the biological reinforced process especially for poisonous and difficult transformation substance has huge potentiality.Alginate calcium due to cost low, active height is the fixation support be most widely used, but shortcoming is that its immobilized microorganism decolorizing effect is lower, and containing multivalent anions (phosphoric acid salt, Citrate trianion, lactic acid salt etc.) and high density ionogen (K
+, Na
+) unstable in solution; Ca
2+easily come off, deliquescing, even to dissolve, limit its application.
Summary of the invention
The object of this invention is to provide a kind of polyurethane foam immobilized microorganism preparation method processing azoic dyestuff sewage, solve existing alginate calcium as the lower problem of its immobilized microorganism decolorizing effect of fixation support.
The technical solution adopted in the present invention is, the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage, and concrete steps are as follows:
Step 1, by polyester polyol, trolamine, water, methyl-silicone oil, dibutyl tin laurate, the graphite felt powder after pulverizing together ultrasonic disperse 5-10 was uniformly mixed after second, then added diphenylmethanediisocyanate MDI, stir 3-5 second to turning white, natural foaming 24h is carried out in rapid transfer, obtains polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side;
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into the sterilizing together of LB substratum, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonas maltophilia strainT-8,25-35 DEG C, rotating speed be 120-140rpm condition under shaking culture 3-5d, with distilled water cleaning for several times, the polyurethane foam of being fixed microorganism.
Feature of the present invention is also,
Polyester polyol in step 1, trolamine, water, methyl-silicone oil, dibutyl tin laurate, diphenylmethanediisocyanate MDI, the volume ratio between the graphite felt powder after pulverizing is 100:2:2:2:1:100:1.
In step 2, the compound method of bacteriolyze meat soup LB substratum is: adopt distilled water by peptone 10g, yeast extract paste 5g, inorganic salt 10g dissolve, and are then settled to 1000mL.
In step 2, sterilizing is sterilizing 20-30min at 115-125 DEG C.
In step 2, microorganism germ oligotrophy unit cell belongs to Stenotrophomonas maltophilia strainT-8 and takes from and be separated in dehydration activity mud after azoic dyestuff is tamed for a long time.
The invention has the beneficial effects as follows, the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage of the present invention, the polyurethane foam of the immobilized microorganism prepared, compared with similar-type products, there is macroreticular structure, specific surface area is high, and with groups such as hydroxyls, can effective fixation of microbe, its physical strength is far above Calcium alginate bead, and antibiont is degraded, the microorganism inoculated in addition is through the rear isolated microorganism with efficient decolorizing degrade azo dyestuff ability of long-term domestication, products obtained therefrom decolouring azoic dyestuff effect increases substantially.
Accompanying drawing explanation
Fig. 1 is the comparison diagram before and after the decolouring of polyurethane foam immobilized microorganism azo dyes;
Fig. 2 is the decolouring comparison diagram of polyurethane foam immobilized microorganism to 5 kinds of azoic dyestuffs;
Fig. 3 is that 16S rRNA sequential analysis constructs phylogenetic tree;
The scanning electron microscope (SEM) photograph of Fig. 4 polyurethane foam immobilized microorganism; Wherein, before a. immobilization, after b. immobilization, after the decolouring of c. immobilization polyurethane foam.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage of the present invention, concrete steps are as follows:
Step 1, by polyester polyol, trolamine, water, methyl-silicone oil, dibutyl tin laurate, graphite felt powder after pulverizing together ultrasonic disperse 5-10 is uniformly mixed (polyester polyol after second, trolamine, water, methyl-silicone oil, dibutyl tin laurate, diphenylmethanediisocyanate MDI, volume ratio between graphite felt powder after pulverizing is 100:2:2:2:1:100:1), then diphenylmethanediisocyanate MDI is added, stir 3-5 second to turning white, natural foaming 24h is carried out in rapid transfer, obtain polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side,
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into LB substratum sterilizing 20 ~ 30min at 115 ~ 125 DEG C together, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonas maltophilia strain T-8,25-35 DEG C, rotating speed be 120-140rpm condition under shaking culture 3-5d, with distilled water cleaning several, the polyurethane foam of being fixed microorganism.
The compound method of bacteriolyze meat soup LB substratum is: adopt distilled water by peptone 10g, yeast extract paste 5g, inorganic salt 10g dissolve, and are then settled to 1000mL.
In step 2, microorganism germ oligotrophy unit cell belongs to Stenotrophomonas maltophilia strainT-8 and takes from and be separated in dehydration activity mud after azoic dyestuff is tamed for a long time.Domestication step: after the dehydration activity mud taking from Sewage Plant sieves, (tropeolin-D, methyl red, gold orange I, orange G, hydrazine Huang, the plain R sodium salt of alizarin yellow is comprised with mixing colouring agent, each concentration is 30mg/L) waste water cultivates altogether, put into the simulation Winogradsky post that volume is 1000ml, after waiting to decolour, supernatant liquor is poured out and adds new same concentration mixed dye wastewater, continue domestication, so multiple circulation of domestication.Then mud is taken out with sterile saline by volume for the ratio of 1:9 mixes, vibrates, leaves standstill.Get supernatant liquor to dilute 100 times the beef extract-peptone that adds with concentration mixing colouring agent of coating is dull and stereotyped afterwards, be seeded in waste water from dyestuff by the bacteria distribution of grow on plates, the bacterial classification getting decolorizing effect optimum carries out next step experiment.
The mechanism of the polyurethane foam immobilized microorganism efficient decolorizing degrade azo dyestuff of process azoic dyestuff sewage is: first to have space many for polyurethane foam, surface-area is large, the characteristics such as high adsorption capacity, more microorganism can be adsorbed, secondly when the active amino on bacterium surface (enzyme) and the free isocyanato of polyurethane foam react, it is firmly incorporated into polyurethane foam surface, mutual adsorpting aggregation simultaneously between microorganism, makes the microbe population be immobilized greatly increase.So the present invention can maintain the cell concentration of greater density, keep efficient bacterium to live, there is stronger shock-resistant ability.
The polyurethane foam treatment based on immobilized microorganisms gold orange I azo dye wastewater utilizing the present invention to prepare:
By gained polyurethane foam immobilized microorganism drying at room temperature, then diameter 5cm is added, fill up to post in the synthetic glass post of high 100cm, add 50mg/l gold orange I azo dye wastewater again to the whole submergence of polyurethane foam immobilized microorganism, then by synthetic glass post horizontal positioned, observe color throw, measure its percent of decolourization.When decolouring is close to after completely, liquid is poured out, adds new azo dye wastewater and carry out second time decolorization experiment.Conclusion is: period 1 percent of decolourization is 96%, and the percent of decolourization of second cycle is 96.2%, illustrates that gained immobilized microorganism has good decolorizing effect to gold orange I, and efficient decolorizing can be kept in a long time active.
Fig. 1 is the comparison diagram before and after the decolouring of polyurethane foam immobilized microorganism azo dyes.Solid line is the length scanning figure before decolouring, and dotted line is the length scanning figure after decolouring.As shown in Figure 1, through the process of immobilized microorganism, the peak value of azoic dyestuff at maximum absorption place occurs significantly to reduce, and illustrates that immobilized microorganism has good decolorizing effect.
Fig. 2 is the decolouring comparison diagram of polyurethane foam immobilized microorganism to 5 kinds of azoic dyestuffs.As shown in Figure 2, immobilized microorganism has good decolorizing effect to tropeolin-D, gold orange I and hydrazine Huang, and percent of decolourization reaches 97.5%, 95.1%, 87.8% respectively.Have certain decolorization to orange G, alizarin yellow element R sodium salt, percent of decolourization can reach 50%.
Fig. 3 is that 16S rRNA sequential analysis constructs phylogenetic tree, the bacterial strain illustrating separation in Fig. 3 and the Phylogenetic Relationships of related strain obtained from GenBank database.The present invention's bacterial classification used is through the bacterial strain with efficient decolorizing azoic dyestuff after domestication separation and Culture, its gene order and Stenotrophomonas maltophilia strain very high homology is found by sequential analysis, thus determine classification and the characteristic of the present invention's bacterial classification used, for the optimization of immobilized microorganism provides reference.
Fig. 4 is the scanning electron microscope (SEM) photograph on polyurethane foam surface.A be immobilization before the scintigram of polyurethane foam, b is the scintigram after polyurethane foam immobilized microorganism, and c is the scintigram after polyurethane foam immobilized microorganism decolouring azoic dyestuff.As shown in the figure, the smooth surface of a, there is no appendix, after immobilized microorganism, its surface there occurs obvious change, illustrate that a large amount of microorganism appendix and polyurethane foam surface are as schemed b, are reduced to some extent by the microorganism on the known polyurethane foam surface after decolouring of figure c, but still have larger amt existence.Illustrate that polyurethane foam immobilized microorganism has good repeatability.
Embodiment 1
Step 1, by polyester polyol 40ml, trolamine 0.8ml, water 0.8ml, methyl-silicone oil 0.8ml, dibutyl tin laurate 0.3ml, 3, the graphite felt powder after pulverizing (3 × 3cm) together ultrasonic disperse was uniformly mixed after 5 seconds, then added diphenylmethanediisocyanate MDI50ml, stir 5 seconds to turning white, natural foaming 24h is carried out in rapid transfer, obtains polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side;
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into LB substratum sterilizing 30min at 115 DEG C together, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonasmaltophilia strain T-8,25 DEG C, rotating speed be 120rpm condition under shaking culture 3d, with distilled water cleaning for several times, the polyurethane foam of being fixed microorganism.
Embodiment 2
Step 1, by polyester polyol 40ml, trolamine 0.8ml, water 0.8ml, methyl-silicone oil 0.8ml, dibutyl tin laurate 0.3ml, 3, the graphite felt powder after pulverizing (3 × 3cm) together ultrasonic disperse was uniformly mixed after 8 seconds, then added diphenylmethanediisocyanate MDI50ml, stir 4 seconds to turning white, natural foaming 24h is carried out in rapid transfer, obtains polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side;
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into LB substratum sterilizing 25min at 120 DEG C together, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonasmaltophilia strain T-8,30 DEG C, rotating speed be 130rpm condition under shaking culture 4d, with distilled water cleaning for several times, the polyurethane foam of being fixed microorganism.
Embodiment 3
Step 1, by polyester polyol 40ml, trolamine 0.8ml, water 0.8ml, methyl-silicone oil 0.8ml, dibutyl tin laurate 0.3ml, 3, the graphite felt powder after pulverizing (3 × 3cm) together ultrasonic disperse was uniformly mixed after 10 seconds, then added diphenylmethanediisocyanate MDI50ml, stir 3 seconds to turning white, natural foaming 24h is carried out in rapid transfer, obtains polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side;
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into LB substratum sterilizing 20min at 125 DEG C together, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonasmaltophilia strain T-8,35 DEG C, rotating speed be 140rpm condition under shaking culture 5d, with distilled water cleaning for several times, the polyurethane foam of being fixed microorganism.
Claims (5)
1. process the polyurethane foam immobilized microorganism preparation method of azoic dyestuff sewage, it is characterized in that, concrete steps are as follows:
Step 1, by polyester polyol, trolamine, water, methyl-silicone oil, dibutyl tin laurate, the graphite felt powder after pulverizing together ultrasonic disperse 5-10 was uniformly mixed after second, then added diphenylmethanediisocyanate MDI, stir 3-5 second to turning white, natural foaming 24h is carried out in rapid transfer, obtains polyurethane foam, the polyurethane foam made is cut into the identical rectangular piece of the length of side;
Step 2, dry after the polyurethane foam distilled water cleaning for several times that step 1 is obtained, preparation bacteriolyze meat soup LB substratum, polyurethane foam is put into the sterilizing together of LB substratum, after cooling, the immobilized microorganism germ oligotrophy unit cell of inoculation belongs to Stenotrophomonas maltophilia strainT-8,25-35 DEG C, rotating speed be 120-140rpm condition under shaking culture 3-5d, with distilled water cleaning for several times, the polyurethane foam of being fixed microorganism.
2. the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage according to claim 1, it is characterized in that, polyester polyol in step 1, trolamine, water, methyl-silicone oil, dibutyl tin laurate, diphenylmethanediisocyanate MDI, the volume ratio between the graphite felt powder after pulverizing is 100:2:2:2:1:100:1.
3. the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage according to claim 1, it is characterized in that, in step 2, the compound method of bacteriolyze meat soup LB substratum is: adopt distilled water by peptone 10g, yeast extract paste 5g, inorganic salt 10g dissolves, and is then settled to 1000mL.
4. the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage according to claim 1, is characterized in that, in step 2, sterilizing is sterilizing 20-30min at 115-125 DEG C.
5. the polyurethane foam immobilized microorganism preparation method of process azoic dyestuff sewage according to claim 1, it is characterized in that, in step 2, microorganism germ oligotrophy unit cell belongs to Stenotrophomonas maltophilia strain T-8 and takes from and be separated in dehydration activity mud after azoic dyestuff is tamed for a long time.
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| CN105461879A (en) * | 2015-11-11 | 2016-04-06 | 浙江省林业科学研究院 | Multipurpose polyurethane effective microorganism solidification carrier |
| CN106256903A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of immobilization method of microorganism based on hyperbranched diazol |
| CN106256902A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of LBL self-assembly process for fixation of microorganism |
| CN106381293A (en) * | 2016-09-07 | 2017-02-08 | 中国海洋大学 | Polysaccharide-polyurethane co-immobilized biological adsorbent and preparation method thereof |
| CN106967641A (en) * | 2017-04-12 | 2017-07-21 | 东华大学 | A kind of micro- acidophilus Stenotrophomonas and its application |
| CN109439711A (en) * | 2018-11-13 | 2019-03-08 | 东北林业大学 | A kind of polyurethane foam immobilized cellulase enzymatic geniposide conversion technique |
| CN110862675A (en) * | 2019-11-27 | 2020-03-06 | 湖北世丰汽车内饰有限公司 | Low-air-permeability polyester sponge and preparation method thereof |
| CN112174325A (en) * | 2020-10-22 | 2021-01-05 | 广东中微环保生物科技有限公司 | Immobilized bioreactor, immobilization method and method for treating black smelly water |
| CN113801820A (en) * | 2021-09-26 | 2021-12-17 | 广东中微环保生物科技有限公司 | Method for screening petroleum degrading bacteria, immobilization method and application of immobilized bacteria agent |
| WO2022219950A1 (en) * | 2021-04-15 | 2022-10-20 | 日清紡ケミカル株式会社 | Microorganism-immobilized carrier for water treatment, flexible polyurethane foam composition, and method for producing flexible polyurethane foam |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106256903A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of immobilization method of microorganism based on hyperbranched diazol |
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| CN106381293B (en) * | 2016-09-07 | 2020-06-02 | 中国海洋大学 | Polysaccharide-polyurethane co-immobilized biological adsorbent and preparation method thereof |
| CN106381293A (en) * | 2016-09-07 | 2017-02-08 | 中国海洋大学 | Polysaccharide-polyurethane co-immobilized biological adsorbent and preparation method thereof |
| CN106967641A (en) * | 2017-04-12 | 2017-07-21 | 东华大学 | A kind of micro- acidophilus Stenotrophomonas and its application |
| CN106967641B (en) * | 2017-04-12 | 2019-11-08 | 东华大学 | A kind of micro- acidophilus Stenotrophomonas and its application |
| CN109439711A (en) * | 2018-11-13 | 2019-03-08 | 东北林业大学 | A kind of polyurethane foam immobilized cellulase enzymatic geniposide conversion technique |
| CN110862675A (en) * | 2019-11-27 | 2020-03-06 | 湖北世丰汽车内饰有限公司 | Low-air-permeability polyester sponge and preparation method thereof |
| CN112174325A (en) * | 2020-10-22 | 2021-01-05 | 广东中微环保生物科技有限公司 | Immobilized bioreactor, immobilization method and method for treating black smelly water |
| WO2022219950A1 (en) * | 2021-04-15 | 2022-10-20 | 日清紡ケミカル株式会社 | Microorganism-immobilized carrier for water treatment, flexible polyurethane foam composition, and method for producing flexible polyurethane foam |
| CN113801820A (en) * | 2021-09-26 | 2021-12-17 | 广东中微环保生物科技有限公司 | Method for screening petroleum degrading bacteria, immobilization method and application of immobilized bacteria agent |
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Application publication date: 20150408 |