CN101734801A - Method for removing 2, 4-dichlorophenol in water by using polyurethane sponge fixed white rot fungi - Google Patents
Method for removing 2, 4-dichlorophenol in water by using polyurethane sponge fixed white rot fungi Download PDFInfo
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- CN101734801A CN101734801A CN200910215720A CN200910215720A CN101734801A CN 101734801 A CN101734801 A CN 101734801A CN 200910215720 A CN200910215720 A CN 200910215720A CN 200910215720 A CN200910215720 A CN 200910215720A CN 101734801 A CN101734801 A CN 101734801A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for removing 2,4-dichlorophenol in water by using polyurethane sponge fixed white rot fungi, belonging to the field of environmental microbiology. The method comprises the following steps: preprocessing a carrier, preparing fixed white rot fungi and removing 2, 4-dichlorophenol in water. The carrier has the characteristics of porosity, hydrophily and good adsorbability, enjoys stable chemical property and hydrolytic resistance, high organism bearing capacity and mass transfer rate and is not soluble in acid/alkaline water solution; while the fixed carrier can effectively absorb and fix white rot fungi, improve capacity of fixed white rot fungi in removing 2,4-dichlorophenol in water and leads the fixed white rot fungi to be easily separated from the product, thus being applicable to execute biological reaction processing on multiple sewages.
Description
Technical field
The present invention relates to a kind of biological fixing carrier, more specifically, the present invention relates to a kind of polyurethane sponge biological fixing carrier, and use this fixation support to remove the method for 2,4 dichloro phenol in the water in conjunction with chemisorption.
Background technology
The chlorophenols material is a class difficult degradation compound, is widely used in the production of wood preservation, sterilant and weedicide for a long time.Wherein, 2,4 dichloro phenol is a kind of pollutent of poisonous, difficult degradation, extensively is present in the factory effluent of agricultural chemicals, dyestuff and softening agent etc.In in the water objectionable impurities or priority pollutant Black List are listed it by country such as the U.S., China.Therefore, how eliminating the pollution of chlorophenols compound in the environment becomes and is subjected to the problem extensively paid attention to.At present, along with improving constantly in the requirement aspect environmental protection and the Sustainable development, the multiple method that chlorophenol pollutes that is used to control occurred, a kind of approach wherein is the water-treatment biological reaction.Although also there are some problems in biological treatment, because its low cost makes it remain the best method that solves the chlorophenols compound pollution problem.
In recent years, manyly studies show that white-rot fungi is very promising microorganism in containing the chlorophenols compound wastewater treatment.White-rot fungi is the filamentous fungus that a class can lignin degrading, because its distinctive lignin-degrading enzymes is, Persistent organic pollutants such as non-specific ground of white-rot fungi energy degrading chlorophenol class, polychlorobiphenyl, polycyclic aromatic hydrocarbons, dyestuff, and chlorophenols compound thoroughly can be degraded to carbonic acid gas and water.If its large-scale application is reacted in water-treatment biological, can effectively control cost of water treatment.But do not have treated white-rot fungi mycelia in the process of growth constantly to extend, the mechanical shear stress that is produced by vibration destroys easily, and then influences its normal growth, and inhibitory enzyme is lived.In order to reach better degradation effect, certainly will need to select specific carrier to fix white-rot fungi, in the hope of chlorophenol pollutant in the degradation water more up hill and dale.
Bio-immobilized technology is to allow the technology of attached growth of microorganisms in carrier by certain immobilization means.Immobilized microorganism technique with its reuse and stable aspect advantage have a good application prospect.According to immobilization carrier and fixed form difference, the biological fixnig method roughly can be divided into four kinds of absorption method, entrapping method, crosslinking and covalent bonds methods.Crosslinking and covalent bonds method all are to utilize two or more functional group preparations, direct and some amino-acid residue of microorganism peptide chain carries out crosslinking reaction, makes microbial immobilized method (for example referring to Chinese patent open file CN 1478734A) thereby form covalent linkage with microorganism.But these two kinds of method chemical reaction fiercenesses are bigger to microorganism active influence, and the linking agent of use is poisonous mostly and cost an arm and a leg, thereby limit its application in practice.Entrapping method is to form with microbial immobilized network, micro-capsule etc. with the macromolecule hydrogel material, or when utilizing water-soluble monomer polymerization formation gel with microorganism embedding (for example referring to Chinese patent open file CN 1277942A) within it.This method is less to the microorganism active influence, but because of the obstruction of its carrier network structure is unfavorable for mass transfer, and the hydrogel shock-resistance is not good, the life-span short.And the support strength that general absorption method is adopted is lower, under anaerobic easily relatively poor by microbiological degradation and mass-transfer performance, easily causes cell inactivation fixedly the time carrying out microorganism.
By contrast, urethane is stable as a family macromolecule material physical and chemical performance, and is cheap, is easy to handle reclaim, and has the potentiality of applied research as cell immobilization carrier.Has following advantage with polyurethane sponge as the fixed biologically carrier: at first be porousness and wetting ability; Secondly, the polyurethane sponge stable chemical performance is not dissolved in acid/alkaline aqueous solution, anti-hydrolysis ability is strong; Moreover, the biological bearing capacity of urethane and rate of mass transfer height, consistency is good, can the active adsorption fixation of microbe, be applicable to that multiple sewage is carried out biological respinse to be handled.In addition, polyurethane sponge has reliable biological safety, is beneficial to attached growth of microorganisms.Up to now, the report of polyurethane sponge as biological fixing carrier also do not appear using.
Summary of the invention
Based on above-mentioned consideration, the purpose of this invention is to provide a kind of utilization and have the method for removing 2,4 dichloro phenol in the water than the bio-carrier fixed white rot fungi of strong adsorptive power.This method can keep polyurethane foam to combine the advantage of disposing of sewage and being had with microorganism, can overcome the deficiency of general process for fixation support strength and mass-transfer performance simultaneously again.This method can be avoided white-rot fungi cell inactivation fixedly the time, improves support strength, can also improve the clearance of immobilizing white rot fungi to 2,4 dichloro phenol.The present invention processes by the raw material of selection carrier and to it and has realized above-mentioned purpose.
According to an aspect of the present invention, the application provides a kind of method that is used for the polyurethane sponge biological fixing carrier of water treatment, and the method comprising the steps of:
1) polyurethane sponge being cut into size is 2 * 1 * 1 cubic centimetre rectangular parallelepiped, under the room temperature, soaks 4 hours in volume fraction is 70% ethanolic soln, removes the sponge chip;
2) with ultrapure water above-mentioned polyurethane sponge is cleaned 3 times, oven temperature is made as 120 ℃ dries;
3) the massive polyurethane sponge that obtains is put into the Erlenmeyer flask that the inorganic salt liquid substratum is housed, add 2 sponges in per 100 milliliters of inorganic salt liquid substratum;
4) supersound process is 30 minutes;
5) 121 ℃ of high-temperature sterilizations are 20 minutes, and sterilization finishes postcooling to room temperature and promptly obtains the polyurethane sponge carrier that immobilization is used;
Good by the carrier surface porousness that aforesaid method obtains, can adsorb fixation of microbe.Described polyurethane sponge carrier is a kind of matrix that is made of sponge plastic, has to allow carrier inside and outside freely to carry out the through hole of liquids and gases exchange.
According to a further aspect in the invention, the application provides immobilizing white rot fungi to remove the method for 2,4 dichloro phenol in the water, and the method comprising the steps of:
1) will under-80 ℃ of conditions, thaw by gradient increased temperature by the white-rot fungi bacterial classification of low tempertaure storage, leave standstill, under aseptic condition, insert in the inorganic salt liquid substratum to room temperature;
2) Erlenmeyer flask that the inorganic salt liquid substratum will be housed is put into the constant temperature shaking table and was left standstill 12 hours, carries out the immobilized reactant of white-rot fungi and carrier, obtains immobilizing white rot fungi;
3) rotating speed of raising shaking table, constant-temperature shaking culture;
4) spawn culture adds 2,4 dichloro phenol waste water to logarithmic growth early stage in Erlenmeyer flask;
5) measure the residual of 2,4 dichloro phenol in 12 hours with high performance liquid chromatograph, with sample under 6000 rev/mins of conditions centrifugal 20 minutes, get supernatant liquor before the sample introduction.
Among the present invention, described inorganic salt liquid substratum moiety is: glucose 10 grams per liters, ammonium tartrate 0.22 grams per liter, potassium primary phosphate 0.2 grams per liter, sal epsom 0.05 grams per liter, calcium chloride 0.01 grams per liter, vitamins B
15 mg/litre.
Among the present invention, described white-rot fungi preferably uses Phanerochaete chrysosporium (Phanerochaete chrysosporium).
Description of drawings
Below in conjunction with drawings and Examples present method is further specified.
Fig. 1 free state and immobilizing white rot fungi degraded 2,4 dichloro phenol (starting point concentration is 10mg/L) are relatively.
Embodiment
Hereinafter will the present invention will be described in detail in conjunction with concrete embodiment, but these descriptions only are exemplary.By being to soak in 70% the ethanolic soln in volume fraction, remove the sponge chip, obtain a kind of urethane biological fixing carrier.It shows porousness and hydrophilic characteristic; Stable chemical performance is not dissolved in acid/alkaline aqueous solution, anti-hydrolysis ability is strong; Biological bearing capacity and rate of mass transfer height, consistency is good, can the active adsorption fixation of microbe, be applicable to that multiple sewage is carried out biological respinse to be handled.In addition, polyurethane sponge has reliable biological safety, is beneficial to attached growth of microorganisms.Present method has successfully realized fixation of white rot fungus cytoactive height and scale preparation.
It is 2 * 1 * 1 cubic centimetre rectangular parallelepiped that polyurethane sponge is cut into size.Under the room temperature, be to soak 4 hours in 70% the ethanolic soln, remove the sponge chip in volume fraction.Above-mentioned polyurethane sponge is cleaned 3 times with ultrapure water, oven temperature is made as 120 ℃ dries.The massive polyurethane sponge that obtains is put into Erlenmeyer flask, add 2 sponges in per 100 milliliters of inorganic salt liquid substratum, regulate pH to 4～6, the ultrasonic cleaner supersound process of 200 watts of power of use, frequency 40 kilohertzs 30 minutes placed 121 ℃ of high-temperature sterilizations 20 minutes.After sterilization finishes and is cooled to room temperature, in the inorganic salt liquid substratum, add aseptic 20% glucose solution with syringe and needle-based strainer (sterilization of band film), under aseptic condition, inoculate white-rot fungi, the shaking table that the Erlenmeyer flask that the inorganic salt liquid substratum will be housed is again put into homo(io)thermism left standstill 12 hours, carried out the immobilized reactant of white-rot fungi and carrier.Rotating speed with shaking table improves then, and constant-temperature shaking culture is cultured to the bacterial classification logarithmic growth in earlier stage, adds finite concentration 2,4 dichloro phenol waste water in the Erlenmeyer flask that contains high-effective microorganism and inorganic salt liquid substratum.Utilize high performance liquid chromatograph to measure the residual of chlorophenol in for some time, with sample under 6000 rev/mins condition centrifugal 2 minutes, get supernatant liquor before the sample introduction.
With the 2,4 dichloro phenol in Phanerochaete chrysosporium (Phanerochaete chrysosporium) degradation water is example:
1. the pre-treatment of polyurethane sponge
1) polyurethane sponge being cut into size is 2 * 1 * 1 cubic centimetre rectangular parallelepiped, under the room temperature, soaks 4 hours in volume fraction is 70% ethanolic soln, removes the sponge chip;
2) with ultrapure water above-mentioned polyurethane sponge is cleaned 3 times, oven temperature is made as 120 ℃ dries;
3) the massive polyurethane sponge that obtains is put into the Erlenmeyer flask that the inorganic salt liquid substratum is housed, add 2 sponges in per 100 milliliters of inorganic salt liquid substratum, regulate pH to 4.5;
4) the ultrasonic cleaner supersound process of 200 watts of power of use, frequency 40 kilohertzs is 30 minutes;
5) 121 ℃ of high-temperature sterilizations are 20 minutes, and sterilization finishes to be cooled to room temperature;
6) 5 milliliters of aseptic quality marks of filtration adding in 100 milliliters of inorganic salt liquid substratum are 20% glucose solution with syringe and needle-based strainer (sterilization of band film), and the glucose final concentration is 4 grams per liters in the maintenance inorganic salt liquid substratum;
7) filtering adding 25 microlitre concentration with syringe and needle-based strainer (sterilization of band film) in 100 milliliters of inorganic salt liquid substratum is the aseptic vitamins B of 100 grams per liters
1Solution keeps vitamins B in the liquid nutrient medium
1Final concentration is 25 mg/litre.
2. the removal of 2,4 dichloro phenol in the preparation of immobilizing white rot fungi and the water
1) will thaw by gradient increased temperature by the white-rot fungi bacterial classification of low tempertaure storage under-80 ℃ of conditions, and leave standstill to room temperature, and insert in the inorganic salt liquid substratum under aseptic condition, inoculum size is 1 * 10
5Individual spore/milliliter;
2) to put into temperature be that 30 ℃ constant temperature shaking table left standstill 12 hours to the Erlenmeyer flask that the inorganic salt liquid substratum will be housed, and carries out the immobilized reactant of white-rot fungi and carrier, obtains immobilizing white rot fungi;
3) rotating speed with shaking table is increased to 160 rev/mins, constant-temperature shaking culture under 30 ℃ of conditions;
4) cultivate after 7 days, add the waste water that contains 2,4 dichloro phenol in the Erlenmeyer flask that contains white-rot fungi and inorganic salt liquid substratum, keeping the starting point concentration of 2,4 dichloro phenol in the interior solution of Erlenmeyer flask is 10 mg/litre;
5) measure the residual of 2,4 dichloro phenol in 12 hours with high performance liquid chromatograph, with sample under 6000 rev/mins of conditions centrifugal 20 minutes, get supernatant liquor before the sample introduction.
Organizing in contrast with free state white-rot fungi and empty carrier (not containing white-rot fungi), is experimental group with the immobilizing white rot fungi, experimental result such as Fig. 1.Experimental result shows that the clearance to 2,4 dichloro phenol in 12 hours has only 14%.Though find in experiment, polyurethane sponge P-Chlorophenol pollutant has certain adsorption effect, adopts the immobilized white-rot fungi of present method that the average removal rate of 2,4 dichloro phenol has been reached more than 79%.And find to adopt the immobilizing white rot fungi of present method preparation agglomerating at the polyurethane sponge surface aggregation in the experiment, be the ellipsoid shape, colony growth is in good condition, has significantly improved the degradation rate of white-rot fungi to 2,4 dichloro phenol.
The beneficial effect of this method is: immobilizing white rot fungi intensity height, and good springiness is difficult for fragmentation, is beneficial to prolonged and repeated use, can effectively reduce production costs, and realizes the scale preparation; And adopt the immobilizing white rot fungi of this method preparation to separate easily with product, also can obtain high-quality product when having simplified separation circuit; In addition, the polyurethane sponge carrier that this method adopts is difficult for being decomposed by microorganism and also is difficult for causing microorganism deactivated, and immobilization is simple to operate, and can significantly improve immobilizing white rot fungi to the degradation rate of 2,4-chlorophenesic acid, has a good application prospect.
Claims (4)
1. method of utilizing polyurethane sponge fixed white rot fungi to remove 2,4 dichloro phenol in the water, the method comprising the steps of:
1) pre-treatment of carrier
A) polyurethane sponge being cut into size is 2 * 1 * 1 cubic centimetre rectangular parallelepiped, under the room temperature, soaks 4 hours in volume fraction is 70% ethanolic soln, removes the sponge chip;
B) with ultrapure water above-mentioned polyurethane sponge is cleaned 3 times, oven temperature is made as 120 ℃ dries;
C) the massive polyurethane sponge that obtains is put into the Erlenmeyer flask that the inorganic salt liquid substratum is housed, add 2 sponges in per 100 milliliters of inorganic salt liquid substratum;
D) supersound process is 30 minutes;
E) 121 ℃ of high-temperature sterilizations are 20 minutes, and sterilization finishes postcooling to room temperature and promptly obtains the polyurethane sponge carrier that immobilization is used;
2) removal of 2,4 dichloro phenol in the immobilization of white-rot fungi and the water
A) will under-80 ℃ of conditions, thaw by gradient increased temperature by the white-rot fungi bacterial classification of low tempertaure storage, leave standstill, under aseptic condition, insert in the inorganic salt liquid substratum to room temperature;
B) Erlenmeyer flask that the inorganic salt liquid substratum will be housed is put into the constant temperature shaking table and was left standstill 12 hours, carries out the immobilized reactant of white-rot fungi and carrier, obtains immobilizing white rot fungi;
C) rotating speed of raising shaking table, constant-temperature shaking culture;
D) spawn culture adds the waste water that contains 2,4 dichloro phenol to logarithmic growth early stage in the Erlenmeyer flask that contains white-rot fungi and inorganic salt liquid substratum;
E) measure the residual of 2,4 dichloro phenol in 12 hours with high performance liquid chromatograph, with sample under 6000 rev/mins of conditions centrifugal 20 minutes, get supernatant liquor before the sample introduction.
2. method according to claim 1 is characterized in that: described polyurethane sponge carrier is a kind of matrix that is made of sponge plastic, has to allow carrier inside and outside freely to carry out the through hole of liquids and gases exchange.
3. method according to claim 1 is characterized in that: described inorganic salt liquid substratum moiety is: glucose 10 grams per liters, ammonium tartrate 0.22 grams per liter, potassium primary phosphate 0.2 grams per liter, sal epsom 0.05 grams per liter, calcium chloride 0.01 grams per liter, vitamins B
15 mg/litre.
4. method according to claim 1 is characterized in that: described white-rot fungi is Phanerochaete chrysosporium (Phanerochaete chrysosporium).
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Cited By (14)
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| CN102399700A (en) * | 2011-11-09 | 2012-04-04 | 武汉工程大学 | Phenol degradation fungus and application thereof |
| CN102701461A (en) * | 2012-06-06 | 2012-10-03 | 安徽科技学院 | Construction method of microbial carrier for wastewater treatment |
| CN102702567A (en) * | 2012-05-18 | 2012-10-03 | 苏州科技学院 | Method for preparing surface function modified polyurethane foaming plastic carriers |
| CN104694527A (en) * | 2015-03-24 | 2015-06-10 | 山东大学 | Method for strengthening sanitary sewage treatment capacity of constructed wetland through fixed type bacillus with polymeric sponges as carrier |
| CN104860369A (en) * | 2015-04-22 | 2015-08-26 | 苏州大学 | Method for adsorption recovery of triclosan in sewage by using penicillium |
| CN105174495A (en) * | 2015-10-23 | 2015-12-23 | 武汉工程大学 | Method for treating chlorinated organic compound wastewater by virtue of biomass carrier immobilized bacteria |
| CN105237122A (en) * | 2015-08-27 | 2016-01-13 | 马鞍山市安康菌业有限公司 | Low-pollution high-effective culture medium capable of effectively preventing and controlling oyster mushroom yellow spot disease and preparation method thereof |
| CN105293715A (en) * | 2015-07-03 | 2016-02-03 | 重庆大学 | Method for controlling water body eutrophication by utilizing immobilized white-rot fungi, and application of method |
| CN106638081A (en) * | 2016-10-28 | 2017-05-10 | 河南华禹环保科技有限公司 | Method for preparing filter paper fiber carrier for white-rot fungus culture |
| CN108017143A (en) * | 2017-12-29 | 2018-05-11 | 南京师范大学 | It is a kind of to aid in Phenol-degrading Bacteria Strains to carry out the biodegradable application of synergy to high concentration phenol using polyurethane sponge |
| CN109111054A (en) * | 2018-09-30 | 2019-01-01 | 北京东方园林环境股份有限公司 | A kind of organic pollution aquifer dystopy Ecosystem restoration system and ecological restoring method |
| CN109354152A (en) * | 2018-12-07 | 2019-02-19 | 四川清和科技有限公司 | It is a kind of using polyurethane as fungi immobilization biological filler of carrier and its preparation method and application |
| CN110894130A (en) * | 2019-12-17 | 2020-03-20 | 内蒙古科技大学 | Device and method for treating phenol-containing coal chemical wastewater by using advanced oxidation method and immobilized white-rot fungi |
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| CN102399700A (en) * | 2011-11-09 | 2012-04-04 | 武汉工程大学 | Phenol degradation fungus and application thereof |
| CN102399700B (en) * | 2011-11-09 | 2013-07-10 | 武汉工程大学 | Phenol degradation fungus and application thereof |
| CN102702567A (en) * | 2012-05-18 | 2012-10-03 | 苏州科技学院 | Method for preparing surface function modified polyurethane foaming plastic carriers |
| CN102701461A (en) * | 2012-06-06 | 2012-10-03 | 安徽科技学院 | Construction method of microbial carrier for wastewater treatment |
| CN104694527A (en) * | 2015-03-24 | 2015-06-10 | 山东大学 | Method for strengthening sanitary sewage treatment capacity of constructed wetland through fixed type bacillus with polymeric sponges as carrier |
| CN104860369A (en) * | 2015-04-22 | 2015-08-26 | 苏州大学 | Method for adsorption recovery of triclosan in sewage by using penicillium |
| CN105293715A (en) * | 2015-07-03 | 2016-02-03 | 重庆大学 | Method for controlling water body eutrophication by utilizing immobilized white-rot fungi, and application of method |
| CN105237122A (en) * | 2015-08-27 | 2016-01-13 | 马鞍山市安康菌业有限公司 | Low-pollution high-effective culture medium capable of effectively preventing and controlling oyster mushroom yellow spot disease and preparation method thereof |
| CN105174495A (en) * | 2015-10-23 | 2015-12-23 | 武汉工程大学 | Method for treating chlorinated organic compound wastewater by virtue of biomass carrier immobilized bacteria |
| CN105174495B (en) * | 2015-10-23 | 2017-06-16 | 武汉工程大学 | The method that biomass carrier immobilization bacterium processes chlorinatedorganic waste water |
| CN106638081A (en) * | 2016-10-28 | 2017-05-10 | 河南华禹环保科技有限公司 | Method for preparing filter paper fiber carrier for white-rot fungus culture |
| CN108017143A (en) * | 2017-12-29 | 2018-05-11 | 南京师范大学 | It is a kind of to aid in Phenol-degrading Bacteria Strains to carry out the biodegradable application of synergy to high concentration phenol using polyurethane sponge |
| CN109111054A (en) * | 2018-09-30 | 2019-01-01 | 北京东方园林环境股份有限公司 | A kind of organic pollution aquifer dystopy Ecosystem restoration system and ecological restoring method |
| CN109354152A (en) * | 2018-12-07 | 2019-02-19 | 四川清和科技有限公司 | It is a kind of using polyurethane as fungi immobilization biological filler of carrier and its preparation method and application |
| CN110894130A (en) * | 2019-12-17 | 2020-03-20 | 内蒙古科技大学 | Device and method for treating phenol-containing coal chemical wastewater by using advanced oxidation method and immobilized white-rot fungi |
| CN117658315A (en) * | 2023-11-20 | 2024-03-08 | 华北电力大学 | Preparation and application of iron-doped carbonized polyanthraquinone loaded polyhexamethylene adipamide fiber filler |
| CN117658315B (en) * | 2023-11-20 | 2024-05-10 | 华北电力大学 | Preparation and application of iron-doped carbonized polyanthraquinone loaded polyhexamethylene adipamide fiber filler |
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Open date: 20100616 |