CN107177588A - Modified glass bead carrier for fixing Azodrin degradation bacteria and preparation method thereof - Google Patents
Modified glass bead carrier for fixing Azodrin degradation bacteria and preparation method thereof Download PDFInfo
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- CN107177588A CN107177588A CN201710635048.3A CN201710635048A CN107177588A CN 107177588 A CN107177588 A CN 107177588A CN 201710635048 A CN201710635048 A CN 201710635048A CN 107177588 A CN107177588 A CN 107177588A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
Abstract
The invention discloses the modified glass bead carrier for fixing Azodrin degradation bacteria.The mixed liquor through the preparation of the carboxylic acid amides of 5 methylpyrazine 2, the carboxylic acid, ethyl ester of 5 Aminopyrazine 2,2 pyrazine t-butyl carboxamides, the nitropyridine of 3 amino 2, the fluorine pyridine of 2 chlorine, 3 nitro 5 and the bromopyridine of 2,5 dichloro 3 is modified after bead is cleaned is prepared into substance B；Mixed liquor of the substance B through PtCl4, AlCl3, Zn (NO3) 2 and Sr (NO3) 2 preparations is modified to be prepared into substance C；The modified obtained material of mixed liquor that substance C is prepared through the bromopyridine of 2 ethyl 5, the ketone of 5,6 dihydro 2H pyrans 2,2 bromoquinolines and the formaldehyde of oxinane 4 is the modified glass bead carrier for being used to fix Azodrin degradation bacteria.
Description
Technical field
It is more particularly to a kind of to be used for admittedly the invention belongs to the research and development of the functional material of environmental pollution treatment technology and preparation field
Determine modified glass bead carrier of Azodrin degradation bacteria and preparation method thereof.
Background technology
Immobilized microorganism technique is the biological skill grown up by the enzyme immobilization technology in biochemical industry in the sixties
Art, by means chemically or physically, free cell is positioned at the area of space of restriction, it is kept activity, can be repeatedly
Utilize.In the seventies later stage, increasingly serious with water pollution, the technology is applied to Industry Waste because of its unique advantage
The biological treatment of water, compared with traditional suspended biological facture, immobilized microorganism technique, which has, improves micro- life in reactor
Thing cell concentration, holding high-efficiency strain, microbe density height and loss are less, reaction speed is fast, resistance to murder by poisoning ability is strong, processing equipment
Simple the advantages of, therefore be always in recent years one of focus of domestic and foreign scholars research, while also achieving encouraging grind
Study carefully achievement.Immobilized microorganism technique can put into practicality it is critical that the selection of fixation support material, is applied to
Microbial immobilized carrier should have that Resistance to microbes, high mechanical strength, mass-transfer performance be good, nontoxic to microorganism, property
The characteristic such as stable, cheap, long lifespan.Currently used fixation support material mainly has：Organic polymer carrier, nothing
Airborne body and complex carrier three major types.But still need and carrier is modified, to improve the activity of carrier fixation of microbe
With performance.
Azodrin is a kind of organophosphorus pesticide of efficient high poison, occupies important in terms of control crop pests and disease pest
Status, gives people to create huge economic benefit and social benefit.With the kind of agricultural chemicals and being continuously increased for usage amount, it is
While agricultural production and income brings guarantee, residues of pesticides also bring serious threat to ecological environment and human health, are to make
Into the principal element of Soil Contamination by Chemical Pesticides, the health of the mankind is directly or indirectly endangered.Azodrin has teratogenesis, carcinogenic, mutagenesis
Effect.Its residual in the environment is eliminated to the degradation property of organophosphorus pesticide using microorganism, with high efficiency, it is low into
The advantages of sheet, non-secondary pollution, thorough degraded, be to repair one of effective way of organophosphorus pesticide pollution soil.Fixed effect long
Phosphorus degradation bacteria is to realize that recovering Azodrin pollutes one of most effective means of environment, still, is also lacked at present for fixed effect long
The functional material of phosphorus degradation bacteria, therefore, develops the modified glass bead carrier for fixing Azodrin degradation bacteria, this for administer and
Azodrin pollution environment is repaired to have great importance.
The content of the invention
It is an object of the invention to provide a kind of modified glass bead carrier for being used to fix Azodrin degradation bacteria, its preparation method
Comprise the following steps that：
(1) to be added to the nitric acid that 150mL mass percent concentrations are 40% molten for the bead for being 2-4mm by 23.6 gram particle footpaths
In liquid, stirred 25 minutes under the conditions of 1000r/min, be filtered to remove liquid, at 101 DEG C after being washed through 500mL deionized waters
Placed 55 minutes in drying box, obtain substance A；
(2) 12.3 grams of 5- methylpyrazine -2- carboxylic acid amides are added in 900mL mass ethanol, shaken in temperature for 30 DEG C
Shaken 35 minutes in bed, 5 parts of equivalent is divided into after shaking up, obtain mixed liquor G1, mixed liquor G2, mixed liquor G3, mixed liquor G4, mixing
Liquid G5；
(3) 8.9 grams of 5- Aminopyrazine -2- carboxylic acid, ethyl esters and 9.1 grams of 2- pyrazine t-butyl carboxamides are added to the chloromethanes of 250mL tri-
In alkane, shaken 35 minutes in temperature is 30 DEG C of shaking table, 5 parts of equivalent be divided into after shaking up, obtain mixed liquor H1, mixed liquor H2,
Mixed liquor H3, mixed liquor H4, mixed liquor H5；
(4) 9.4 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.3 grams of 2- are added to mixed liquor G1
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J1；
(5) mixed liquor J1 and the chloro- 3- bromopyridines of 9.9 grams of 2,5- bis- are added in mixed liquor H1, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K1；
(6) substance A is added in mixed liquor K1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance A 1, and substance A 1 is placed 55 minutes in 101 DEG C of drying box, substance A 2 is obtained；
(7) 9.1 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.0 grams of 2- are added to mixed liquor G2
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J2；
(8) mixed liquor J2 and the chloro- 3- bromopyridines of 9.6 grams of 2,5- bis- are added in mixed liquor H2, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K2；
(9) substance A 2 is added in mixed liquor K2, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance A 3, and substance A 3 is placed 55 minutes in 101 DEG C of drying box, substance A 4 is obtained；
(10) 8.8 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.7 grams of 2- are added to mixed liquor G3
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J3；
(11) mixed liquor J3 and the chloro- 3- bromopyridines of 9.3 grams of 2,5- bis- are added in mixed liquor H3, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K3；
(12) substance A 4 is added in mixed liquor K3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 5, and substance A 5 is placed 55 minutes in 101 DEG C of drying box, substance A 6 is obtained；
(13) 8.5 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.4 grams of 2- are added to mixed liquor G4
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J4；
(14) mixed liquor J4 and the chloro- 3- bromopyridines of 9.0 grams of 2,5- bis- are added in mixed liquor H4, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K4；
(15) substance A 6 is added in mixed liquor K4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 7, and substance A 7 is placed 55 minutes in 101 DEG C of drying box, substance A 8 is obtained；
(16) 8.2 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.1 grams of 2- are added to mixed liquor G5
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J5；
(17) mixed liquor J5 and the chloro- 3- bromopyridines of 8.7 grams of 2,5- bis- are added in mixed liquor H5, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K5；
(18) substance A 8 is added in mixed liquor K5, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 9, and substance A 9 is placed 55 minutes in 101 DEG C of drying box, substance B is obtained；
(19) by 1.64 grams of PtCl4With 2.87 grams of AlCl3It is added in 800mL deionized waters, under the conditions of 1000r/min
Stirring 3 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5 after shaking up；
(20) by Zn (NO of the 140mL molar concentrations for 0.42mol/L3)2Solution and 60mL molar concentrations are 0.53mol/L
Sr (NO3)2Solution is added in mixed liquor L1, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M1, with mole
Concentration is that mixed liquor M1 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N1；
(21) substance B is added in mixed liquor N1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance B 1, and substance B 1 is put after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Put 55 minutes, obtain substance B 2；
(22) by Zn (NO of the 140mL molar concentrations for 0.47mol/L3)2Solution and 60mL molar concentrations are 0.48mol/L
Sr (NO3)2Solution is added in mixed liquor L2, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M2, with mole
Concentration is that mixed liquor M2 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N2；
(23) substance B 2 is added in mixed liquor N2, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 3, and substance B 3 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 4；
(24) by Zn (NO of the 140mL molar concentrations for 0.52mol/L3)2Solution and 60mL molar concentrations are 0.43mol/L
Sr (NO3)2Solution is added in mixed liquor L3, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M3, with mole
Concentration is that mixed liquor M3 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N3；
(25) substance B 4 is added in mixed liquor N3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 5, and substance B 5 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 6；
(26) by Zn (NO of the 140mL molar concentrations for 0.57mol/L3)2Solution and 60mL molar concentrations are 0.38mol/L
Sr (NO3)2Solution is added in mixed liquor L4, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M4, with mole
Concentration is that mixed liquor M4 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N4；
(27) substance B 6 is added in mixed liquor N4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 7, and substance B 7 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 8；
(28) by Zn (NO of the 140mL molar concentrations for 0.62mol/L3)2Solution and 60mL molar concentrations are 0.33mol/L
Sr (NO3)2Solution is added in mixed liquor L5, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M5, with mole
Concentration is that mixed liquor M5 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N5；
(29) substance B 8 is added in mixed liquor N5, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 9, and substance B 9 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C；
(30) 14.6 grams of 2- ethyl -5- bromopyridines are added under 1000r/min stirring conditions in 800mL ethanol,
Then temperature adds 8.2 grams of 5,6- dihydro -2H- pyran-2-ones, is divided into after shaking up to be shaken in 30 DEG C of shaking table 15 minutes
4 parts of amount, obtains mixed liquor P1, mixed liquor P2, mixed liquor P3, mixed liquor P4；
(31) 3.9 grams of 2- bromoquinolines and 7.7 grams of oxinane -4- formaldehyde are added in mixed liquor P1, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q1；
(32) substance C is added in mixed liquor Q1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance C 1, and substance C 1 is put after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Put 55 minutes, obtain substance C 2；
(33) 3.6 grams of 2- bromoquinolines and 7.4 grams of oxinane -4- formaldehyde are added in mixed liquor P2, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q2；
(34) substance C 2 is added in mixed liquor Q2, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 3, and substance C 3 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C 4；
(35) 3.3 grams of 2- bromoquinolines and 7.1 grams of oxinane -4- formaldehyde are added in mixed liquor P3, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q3；
(36) substance C 4 is added in mixed liquor Q3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 5, and substance C 5 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C 6；
(37) 3.0 grams of 2- bromoquinolines and 6.8 grams of oxinane -4- formaldehyde are added in mixed liquor P4, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q4；
(38) substance C 6 is added in mixed liquor Q4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 7, and substance C 7 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtained material is the modified glass bead carrier for being used to fix Azodrin degradation bacteria.
The beneficial effects of the invention are as follows the obtained modified glass bead carrier for being used to fix Azodrin degradation bacteria has machinery
Intensity is high, mass-transfer performance is good, property is stable, long lifespan the features such as.
Embodiment
The invention provides a kind of modified glass bead carrier for being used to fix Azodrin degradation bacteria, below by an example
To illustrate to apply process in fact.
Embodiment 1.
(1) to be added to the nitric acid that 150mL mass percent concentrations are 40% molten for the bead for being 2-4mm by 23.6 gram particle footpaths
In liquid, stirred 25 minutes under the conditions of 1000r/min, be filtered to remove liquid, at 101 DEG C after being washed through 500mL deionized waters
Placed 55 minutes in drying box, obtain substance A；
(2) 12.3 grams of 5- methylpyrazine -2- carboxylic acid amides are added in 900mL mass ethanol, shaken in temperature for 30 DEG C
Shaken 35 minutes in bed, 5 parts of equivalent is divided into after shaking up, obtain mixed liquor G1, mixed liquor G2, mixed liquor G3, mixed liquor G4, mixing
Liquid G5；
(3) 8.9 grams of 5- Aminopyrazine -2- carboxylic acid, ethyl esters and 9.1 grams of 2- pyrazine t-butyl carboxamides are added to the chloromethanes of 250mL tri-
In alkane, shaken 35 minutes in temperature is 30 DEG C of shaking table, 5 parts of equivalent be divided into after shaking up, obtain mixed liquor H1, mixed liquor H2,
Mixed liquor H3, mixed liquor H4, mixed liquor H5；
(4) 9.4 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.3 grams of 2- are added to mixed liquor G1
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J1；
(5) mixed liquor J1 and the chloro- 3- bromopyridines of 9.9 grams of 2,5- bis- are added in mixed liquor H1, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K1；
(6) substance A is added in mixed liquor K1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance A 1, and substance A 1 is placed 55 minutes in 101 DEG C of drying box, substance A 2 is obtained；
(7) 9.1 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.0 grams of 2- are added to mixed liquor G2
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J2；
(8) mixed liquor J2 and the chloro- 3- bromopyridines of 9.6 grams of 2,5- bis- are added in mixed liquor H2, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K2；
(9) substance A 2 is added in mixed liquor K2, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance A 3, and substance A 3 is placed 55 minutes in 101 DEG C of drying box, substance A 4 is obtained；
(10) 8.8 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.7 grams of 2- are added to mixed liquor G3
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J3；
(11) mixed liquor J3 and the chloro- 3- bromopyridines of 9.3 grams of 2,5- bis- are added in mixed liquor H3, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K3；
(12) substance A 4 is added in mixed liquor K3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 5, and substance A 5 is placed 55 minutes in 101 DEG C of drying box, substance A 6 is obtained；
(13) 8.5 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.4 grams of 2- are added to mixed liquor G4
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J4；
(14) mixed liquor J4 and the chloro- 3- bromopyridines of 9.0 grams of 2,5- bis- are added in mixed liquor H4, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K4；
(15) substance A 6 is added in mixed liquor K4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 7, and substance A 7 is placed 55 minutes in 101 DEG C of drying box, substance A 8 is obtained；
(16) 8.2 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.1 grams of 2- are added to mixed liquor G5
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J5；
(17) mixed liquor J5 and the chloro- 3- bromopyridines of 8.7 grams of 2,5- bis- are added in mixed liquor H5, are 30 DEG C in temperature
Shaken 35 minutes in shaking table, obtain mixed liquor K5；
(18) substance A 8 is added in mixed liquor K5, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance A 9, and substance A 9 is placed 55 minutes in 101 DEG C of drying box, substance B is obtained；
(19) by 1.64 grams of PtCl4With 2.87 grams of AlCl3It is added in 800mL deionized waters, under the conditions of 1000r/min
Stirring 3 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5 after shaking up；
(20) by Zn (NO of the 140mL molar concentrations for 0.42mol/L3)2Solution and 60mL molar concentrations are 0.53mol/L
Sr (NO3)2Solution is added in mixed liquor L1, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M1, with mole
Concentration is that mixed liquor M1 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N1；
(21) substance B is added in mixed liquor N1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance B 1, and substance B 1 is put after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Put 55 minutes, obtain substance B 2；
(22) by Zn (NO of the 140mL molar concentrations for 0.47mol/L3)2Solution and 60mL molar concentrations are 0.48mol/L
Sr (NO3)2Solution is added in mixed liquor L2, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M2, with mole
Concentration is that mixed liquor M2 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N2；
(23) substance B 2 is added in mixed liquor N2, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 3, and substance B 3 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 4；
(24) by Zn (NO of the 140mL molar concentrations for 0.52mol/L3)2Solution and 60mL molar concentrations are 0.43mol/L
Sr (NO3)2Solution is added in mixed liquor L3, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M3, with mole
Concentration is that mixed liquor M3 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N3；
(25) substance B 4 is added in mixed liquor N3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 5, and substance B 5 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 6；
(26) by Zn (NO of the 140mL molar concentrations for 0.57mol/L3)2Solution and 60mL molar concentrations are 0.38mol/L
Sr (NO3)2Solution is added in mixed liquor L4, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M4, with mole
Concentration is that mixed liquor M4 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N4；
(27) substance B 6 is added in mixed liquor N4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 7, and substance B 7 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance B 8；
(28) by Zn (NO of the 140mL molar concentrations for 0.62mol/L3)2Solution and 60mL molar concentrations are 0.33mol/L
Sr (NO3)2Solution is added in mixed liquor L5, under the conditions of 1000r/min stir 3 minutes, obtain mixed liquor M5, with mole
Concentration is that mixed liquor M5 pH value is adjusted to 6.8~7.2 by 0.01mol/L hydrochloric acid solution and 0.01mol/L NaOH solution, is obtained
To mixed liquor N5；
(29) substance B 8 is added in mixed liquor N5, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance B 9, and substance B 9 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C；
(30) 14.6 grams of 2- ethyl -5- bromopyridines are added under 1000r/min stirring conditions in 800mL ethanol,
Then temperature adds 8.2 grams of 5,6- dihydro -2H- pyran-2-ones, is divided into after shaking up to be shaken in 30 DEG C of shaking table 15 minutes
4 parts of amount, obtains mixed liquor P1, mixed liquor P2, mixed liquor P3, mixed liquor P4；
(31) 3.9 grams of 2- bromoquinolines and 7.7 grams of oxinane -4- formaldehyde are added in mixed liquor P1, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q1；
(32) substance C is added in mixed liquor Q1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Body obtains substance C 1, and substance C 1 is put after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Put 55 minutes, obtain substance C 2；
(33) 3.6 grams of 2- bromoquinolines and 7.4 grams of oxinane -4- formaldehyde are added in mixed liquor P2, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q2；
(34) substance C 2 is added in mixed liquor Q2, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 3, and substance C 3 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C 4；
(35) 3.3 grams of 2- bromoquinolines and 7.1 grams of oxinane -4- formaldehyde are added in mixed liquor P3, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q3；
(36) substance C 4 is added in mixed liquor Q3, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 5, and substance C 5 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtain substance C 6；
(37) 3.0 grams of 2- bromoquinolines and 6.8 grams of oxinane -4- formaldehyde are added in mixed liquor P4, are 30 in temperature
DEG C shaking table in shake 25 minutes, obtain mixed liquor Q4；
(38) substance C 6 is added in mixed liquor Q4, shakes 15 minutes, be filtered to remove in temperature is 30 DEG C of shaking table
Liquid obtains substance C 7, and substance C 7 is after the ethanol washing that 100mL mass percent concentrations are 95% in 105 DEG C of drying box
Place 55 minutes, obtained material is the modified glass bead carrier for being used to fix Azodrin degradation bacteria.
Azodrin is degraded with the modified glass bead carrier for being used to fix Azodrin degradation bacteria made from the inventive method
Bacterium has carried out immobilization, and has carried out degradation experiment to Azodrin polluted-water with the Azodrin degradation bacteria after fixed, as a result table
It is bright：When the initial concentration of Azodrin is 43.7mg/L, the concentration drop of Azodrin degradation bacteria Azodrin after 4 days after fixing is added
It is low to arrive 0.2mg/L.
Claims (1)
1. a kind of modified glass bead carrier for being used to fix Azodrin degradation bacteria, it is characterised in that prepare modified glass pearl load
Body method is comprised the following steps that：
(1) bead for being 2-4mm by 23.6 gram particle footpaths is added to the salpeter solution that 150mL mass percent concentrations are 40%
In, stirred 25 minutes under the conditions of 1000r/min, be filtered to remove liquid, it is dry at 101 DEG C after being washed through 500mL deionized waters
Placed 55 minutes in dry case, obtain substance A；
(2) 12.3 grams of 5- methylpyrazine -2- carboxylic acid amides are added in 900mL mass ethanol, in temperature in 30 DEG C of shaking table
Shake 35 minutes, 5 parts of equivalent is divided into after shaking up, mixed liquor G1, mixed liquor G2, mixed liquor G3, mixed liquor G4, mixed liquor is obtained
G5；
(3) 8.9 grams of 5- Aminopyrazine -2- carboxylic acid, ethyl esters and 9.1 grams of 2- pyrazine t-butyl carboxamides are added to 250mL chloroforms
In, shaken 35 minutes in temperature is 30 DEG C of shaking table, 5 parts of equivalent is divided into after shaking up, obtained mixed liquor H1, mixed liquor H2, mix
Close liquid H3, mixed liquor H4, mixed liquor H5；
(4) 9.4 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.3 grams of 2- are added in mixed liquor G1,
Temperature obtains mixed liquor J1 to be shaken 35 minutes in 30 DEG C of shaking table；
(5) mixed liquor J1 and the chloro- 3- bromopyridines of 9.9 grams of 2,5- bis- are added in mixed liquor H1, in the shaking table that temperature is 30 DEG C
It is middle to shake 35 minutes, obtain mixed liquor K1；
(6) substance A is added in mixed liquor K1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid and obtain
To substance A 1, substance A 1 is placed 55 minutes in 101 DEG C of drying box, substance A 2 is obtained；
(7) 9.1 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 8.0 grams of 2- are added in mixed liquor G2,
Temperature obtains mixed liquor J2 to be shaken 35 minutes in 30 DEG C of shaking table；
(8) mixed liquor J2 and the chloro- 3- bromopyridines of 9.6 grams of 2,5- bis- are added in mixed liquor H2, in the shaking table that temperature is 30 DEG C
It is middle to shake 35 minutes, obtain mixed liquor K2；
(9) substance A 2 is added in mixed liquor K2, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid and obtain
To substance A 3, substance A 3 is placed 55 minutes in 101 DEG C of drying box, substance A 4 is obtained；
(10) 8.8 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.7 grams of 2- are added in mixed liquor G3,
Shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J3；
(11) mixed liquor J3 and the chloro- 3- bromopyridines of 9.3 grams of 2,5- bis- are added in mixed liquor H3, in the shaking table that temperature is 30 DEG C
It is middle to shake 35 minutes, obtain mixed liquor K3；
(12) substance A 4 is added in mixed liquor K3, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance A 5 is obtained, substance A 5 is placed 55 minutes in 101 DEG C of drying box, substance A 6 is obtained；
(13) 8.5 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.4 grams of 2- are added in mixed liquor G4,
Shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J4；
(14) mixed liquor J4 and the chloro- 3- bromopyridines of 9.0 grams of 2,5- bis- are added in mixed liquor H4, in the shaking table that temperature is 30 DEG C
It is middle to shake 35 minutes, obtain mixed liquor K4；
(15) substance A 6 is added in mixed liquor K4, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance A 7 is obtained, substance A 7 is placed 55 minutes in 101 DEG C of drying box, substance A 8 is obtained；
(16) 8.2 grams of 3- amino -2- nitropyridines and the chloro- 3- nitros -5- fluorine pyridines of 7.1 grams of 2- are added in mixed liquor G5,
Shaken 35 minutes in temperature is 30 DEG C of shaking table, obtain mixed liquor J5；
(17) mixed liquor J5 and the chloro- 3- bromopyridines of 8.7 grams of 2,5- bis- are added in mixed liquor H5, in the shaking table that temperature is 30 DEG C
It is middle to shake 35 minutes, obtain mixed liquor K5；
(18) substance A 8 is added in mixed liquor K5, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance A 9 is obtained, substance A 9 is placed 55 minutes in 101 DEG C of drying box, substance B is obtained；
(19) by 1.64 grams of PtCl4With 2.87 grams of AlCl3It is added in 800mL deionized waters, 3 is stirred under the conditions of 1000r/min
Minute, 5 parts of equivalent is divided into after shaking up, mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5 is obtained；
(20) by Zn (NO of the 140mL molar concentrations for 0.42mol/L3)2Solution and the Sr that 60mL molar concentrations are 0.53mol/L
(NO3)2Solution is added in mixed liquor L1, is stirred 3 minutes under the conditions of 1000r/min, is obtained mixed liquor M1, use molar concentration
Mixed liquor M1 pH value is adjusted to 6.8~7.2 by the NaOH solution of hydrochloric acid solution and 0.01mol/L for 0.01mol/L, is mixed
Close liquid N1；
(21) substance B is added in mixed liquor N1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid and obtain
To substance B 1, substance B 1 places 55 after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Minute, obtain substance B 2；
(22) by Zn (NO of the 140mL molar concentrations for 0.47mol/L3)2Solution and the Sr that 60mL molar concentrations are 0.48mol/L
(NO3)2Solution is added in mixed liquor L2, is stirred 3 minutes under the conditions of 1000r/min, is obtained mixed liquor M2, use molar concentration
Mixed liquor M2 pH value is adjusted to 6.8~7.2 by the NaOH solution of hydrochloric acid solution and 0.01mol/L for 0.01mol/L, is mixed
Close liquid N2；
(23) substance B 2 is added in mixed liquor N2, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance B 3 is obtained, substance B 3 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance B 4；
(24) by Zn (NO of the 140mL molar concentrations for 0.52mol/L3)2Solution and the Sr that 60mL molar concentrations are 0.43mol/L
(NO3)2Solution is added in mixed liquor L3, is stirred 3 minutes under the conditions of 1000r/min, is obtained mixed liquor M3, use molar concentration
Mixed liquor M3 pH value is adjusted to 6.8~7.2 by the NaOH solution of hydrochloric acid solution and 0.01mol/L for 0.01mol/L, is mixed
Close liquid N3；
(25) substance B 4 is added in mixed liquor N3, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance B 5 is obtained, substance B 5 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance B 6；
(26) by Zn (NO of the 140mL molar concentrations for 0.57mol/L3)2Solution and the Sr that 60mL molar concentrations are 0.38mol/L
(NO3)2Solution is added in mixed liquor L4, is stirred 3 minutes under the conditions of 1000r/min, is obtained mixed liquor M4, use molar concentration
Mixed liquor M4 pH value is adjusted to 6.8~7.2 by the NaOH solution of hydrochloric acid solution and 0.01mol/L for 0.01mol/L, is mixed
Close liquid N4；
(27) substance B 6 is added in mixed liquor N4, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance B 7 is obtained, substance B 7 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance B 8；
(28) by Zn (NO of the 140mL molar concentrations for 0.62mol/L3)2Solution and the Sr that 60mL molar concentrations are 0.33mol/L
(NO3)2Solution is added in mixed liquor L5, is stirred 3 minutes under the conditions of 1000r/min, is obtained mixed liquor M5, use molar concentration
Mixed liquor M5 pH value is adjusted to 6.8~7.2 by the NaOH solution of hydrochloric acid solution and 0.01mol/L for 0.01mol/L, is mixed
Close liquid N5；
(29) substance B 8 is added in mixed liquor N5, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance B 9 is obtained, substance B 9 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance C；
(30) 14.6 grams of 2- ethyl -5- bromopyridines are added under 1000r/min stirring conditions in 800mL ethanol, in temperature
To be shaken in 30 DEG C of shaking tables 15 minutes, 8.2 grams of 5,6- dihydro -2H- pyran-2-ones are then added, equivalent 4 is divided into after shaking up
Part, obtain mixed liquor P1, mixed liquor P2, mixed liquor P3, mixed liquor P4；
(31) 3.9 grams of 2- bromoquinolines and 7.7 grams of oxinane -4- formaldehyde are added in mixed liquor P1, are 30 DEG C in temperature
Shaken 25 minutes in shaking table, obtain mixed liquor Q1；
(32) substance C is added in mixed liquor Q1, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid and obtain
To substance C 1, substance C 1 places 55 after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
Minute, obtain substance C 2；
(33) 3.6 grams of 2- bromoquinolines and 7.4 grams of oxinane -4- formaldehyde are added in mixed liquor P2, are 30 DEG C in temperature
Shaken 25 minutes in shaking table, obtain mixed liquor Q2；
(34) substance C 2 is added in mixed liquor Q2, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance C 3 is obtained, substance C 3 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance C 4；
(35) 3.3 grams of 2- bromoquinolines and 7.1 grams of oxinane -4- formaldehyde are added in mixed liquor P3, are 30 DEG C in temperature
Shaken 25 minutes in shaking table, obtain mixed liquor Q3；
(36) substance C 4 is added in mixed liquor Q3, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance C 5 is obtained, substance C 5 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtain substance C 6；
(37) 3.0 grams of 2- bromoquinolines and 6.8 grams of oxinane -4- formaldehyde are added in mixed liquor P4, are 30 DEG C in temperature
Shaken 25 minutes in shaking table, obtain mixed liquor Q4；
(38) substance C 6 is added in mixed liquor Q4, is shaken 15 minutes in temperature is 30 DEG C of shaking table, be filtered to remove liquid
Substance C 7 is obtained, substance C 7 is placed after being washed through 100mL mass percent concentrations for 95% ethanol in 105 DEG C of drying box
55 minutes, obtained material was the modified glass bead carrier for being used to fix Azodrin degradation bacteria.
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| CN108164000A (en) * | 2017-12-28 | 2018-06-15 | 光合强化（北京）生物科技有限公司 | Glass plate of fixed ammonia oxidizing bacteria and preparation method thereof |
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