CN108425130B - The method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate - Google Patents
The method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate Download PDFInfo
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- CN108425130B CN108425130B CN201810323258.3A CN201810323258A CN108425130B CN 108425130 B CN108425130 B CN 108425130B CN 201810323258 A CN201810323258 A CN 201810323258A CN 108425130 B CN108425130 B CN 108425130B
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Abstract
The present invention provides a kind of method of the micro-reduction dehalogenation of halogenated aromatic pollutant that electrochemistry promotes humus to mediate, and belongs to living resources technical field.Method is conducting resinl to be applied to the surface of graphite electrode, and humus is adhered to the surface of conducting resinl.The graphite electrode for adhering to humus and Ag/AgCl saturation electrode are placed in catholyte, platinum electrode is placed in anolyte.Electrochemical workstation connects graphite electrode, Ag/AgCl saturation electrode and platinum electrode, is persistently powered 7~9 days to the external voltage that working electrode imposes -600~-700mV.It wherein, include microorganism and halogenated aromatic compound in catholyte.The method can promote the halogenated aromatic compound in catholyte to carry out micro-reduction dehalogenation, solid-state humus is restored by graphite electrode, microorganism carries out reductive dehalogenation using the solid-state humus after reduction as electron donor, to halogenated aromatic compound.
Description
Technical field
The present invention relates to living resources technical field, the halogen for promoting humus to mediate in particular to a kind of electrochemistry
For the method for the micro-reduction dehalogenation of aromatic pollution.
Background technique
Humus (English claims Humus) definition: organism in heaven forms through microorganism decomposition organic in the soil
Substance.Dark brown can improve soil containing some elements required for plant growth and development, increase fertility, and main method is side
The gap for helping increase that air and water can be allowed to enter, it is also the same to generate the necessary nitrogen of plant, sulphur, potassium and phosphorus.Plant and animal residues
Complicated high-molecular compound is synthesized again while forming simple compounds under microbial action.
Solid-state humus is not fixed in the prior art and passes through what electrochemical means promotion humus mediated on the electrode
Research of the microorganism to the method for halogenated aromatic pollutant anaerobic reduction dehalogenation.
Summary of the invention
The purpose of the present invention is to provide a kind of micro- lifes for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate
The method of object reductive dehalogenation, can effectively facilitate to the halogenated aromatic substance in bioelectrochemical system in catholyte into
Row reductive dehalogenation.
Realization that the present invention adopts the following technical solutions:
The microorganism that a kind of electrochemistry promotes solid-state humus to mediate is to halogenated aromatic pollutant anaerobic reduction dehalogenation
Method includes the following steps:
(1), conducting resinl is applied to the surface of graphite electrode, and humus is adhered to the surface of conducting resinl;
(2), the graphite electrode for adhering to humus and Ag/AgCl saturation electrode are placed in the cathode chamber containing catholyte
It is interior, platinum electrode is placed in the anode chamber containing anolyte, cathode chamber and anode chamber are carried out by cation-exchange membrane
Separate;
(3), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum electrode, constitute three electrode of dual chamber
System is persistently powered to the external voltage that working electrode imposes -600~-700mV 7~9 days;
Wherein, catholyte includes microorganism and halogenated aromatic compound;Anolyte includes inorganic salts culture
Base.
Further, in preferred embodiments of the present invention, above-mentioned humus is humin.
Further, in preferred embodiments of the present invention, above-mentioned catholyte further includes minimal medium, formic acid
Salt and vitamin.
Further, in preferred embodiments of the present invention, above-mentioned minimal medium include mass concentration be 1.0~
The NH of 1.5g/L4The CaCl of Cl, 0.04~0.08g/L2·2H2O, the MgCl of 0.08~0.12g/L2·6H2O, 0.4~0.8g/L
K2HPO4。
Further, in preferred embodiments of the present invention, above-mentioned minimal medium further includes the micro of 1~3ml/L
Element S L-10 solution, the Se/W solution of 1~3ml/L and 15~20ml/L MOPS buffer.
Further, in preferred embodiments of the present invention, mentioned microorganism includes dehalogenation bacillus, bacteroid, sulphur list
Born of the same parents bacterium and desulfovibrio.
Further, in preferred embodiments of the present invention, mentioned microorganism is counted according to quantity part, including dehalogenation bacillus 2
~3 parts, 1~2 part of bacteroid, 3~4 parts of sulphur monad and 2~3 parts of desulfovibrio.
Further, in preferred embodiments of the present invention, above-mentioned conducting resinl is silver conductive adhesive or carbonaceous conductive glue.
Further, in preferred embodiments of the present invention, the mass ratio of above-mentioned humin and conducting resinl be 1:(10~
15)。
It further, further include that will adhere to humic before step (2) in step (1) in preferred embodiments of the present invention
The step of conducting resinl of matter and the graphite electrode for smearing conducting resinl place 8~12h at room temperature.
The beneficial effect of the method for the halogenated aromatic reductive dehalogenation that presently preferred embodiments of the present invention provides is: by conducting resinl
It is applied to the surface of graphite electrode, and humus is adhered to the surface of conducting resinl, conducting resinl is used as graphite electrode and humic
The medium that matter connects, humus directly cannot make humic by the setting of conducting resinl by anodizing and reduction well
Matter can be stably adhered to electrode surface efficiently by anodizing and reduction.The graphite electrode and Ag/ of humus will be adhered to
AgCl saturation electrode is placed in the cathode chamber containing catholyte, and platinum electrode is placed in the anode chamber containing anolyte
Interior, cathode chamber and anode chamber are separated by cation-exchange membrane.It is full that electrochemical workstation connects graphite electrode, Ag/AgCl
With electrode and platinum electrode, using graphite electrode as working electrode, Ag/AgCl is saturated electrode as reference electrode, platinum electrode
As to electrode, dual chamber three-electrode system is constituted, 7 are persistently powered to the external voltage that working electrode imposes -600~-700mV~
9 days, wherein contain microorganism and halogenated aromatic compound in catholyte, apply negative voltage, solid-state humic can be restored
Solid-state humus is fixed on graphite electrode by matter, restores solid-state humus by graphite electrode, micro- life in catholyte
Object restores the halogenated aromatic compound in catholyte as electron donor using the solid-state humus after reduction
Dehalogenation.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The microorganism for the halogenated aromatic pollutant for promoting humus to mediate the electrochemistry of the embodiment of the present invention below is also
The method of former dehalogenation is specifically described.
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps:
(1), conducting resinl is applied to the surface of graphite electrode, and humus is adhered to the surface of conducting resinl.
For conducting resinl as the medium for connecting graphite electrode and humus, humus directly cannot be well by electrode
Oxidation or reduction, by the setting of conducting resinl, allow humus to be stably adhered to electrode surface efficiently by anodizing
And reduction.
Preferably, conducting resinl is silver conductive adhesive or carbonaceous conductive glue, is arranged in conducting resinl using silver or carbon as conductive filler,
Form conductive path.Carbon is arranged on graphite electrode as conductive filler, new conductive impurity will not be introduced in electrode surface,
Electrochemical reaction occurs in the electrolytic solution to interfere graphite electrode to the electron transmission of humus.
Preferably, humus is humin.Humin be humus in conjunction with soil mineral most close component, most
Stablize, be most not susceptible to redox reaction, the researches of electro-chemical activity are carried out to it, currently without being fixed in stone
The research that its electro-chemical activity is carried out on electrode ink.
Humus is humin, keeps research of the invention more valuable, meanwhile, humin is fixed on graphite electrode can be with
Electrochemical reaction more efficiently occurs with electrode.
Preferably, the mass ratio of humin and conducting resinl is 1:(10~15).Enable humin to be uniformly adhered leading
On electric glue, subsequent humin is facilitated to be fixed on graphite electrode, keeps the fixed effect of humin more preferable.
In the present invention, the extracting method of humin is: weigh river sediments dry in right amount, after being mixed with aqueous slkali
6~8h is shaken in the case where logical nitrogen, and is centrifugated, casts out supernatant and bottom sand, middle layer is taken to glue shape deposit, and
Freeze-drying obtains humin.
Preferably, the partial size of river sediments is not more than 50 mesh, and river silt powder more uniform can be mixed with aqueous slkali,
More humins can be extracted by making in river silt powder comes out.Due to there is many substances in river silt, it may occur that oxidation reaction
And the extraction of humin is influenced, it is shaken in the case where logical nitrogen, keeps the extraction effect of humin more preferable.
Preferably, aqueous slkali is alkaline sodium salt solution, more preferable using extraction effect of the sodium salt solution to humin.With alkalinity
Potassium salt soln is compared, and the alkalinity of alkaline sodium salt solution is slightly weak, is avoided humin that alkalinity occurs and is destroyed, improves the extraction of humin
Amount.
Alkaline sodium salt solution can be highly basic salt, such as: sodium hydroxide is also possible to strong base-weak acid salt, such as: sodium carbonate, phosphorus
Sour sodium, sodium bicarbonate and sodium pyrophosphate etc..With certain alkalinity, humin is extracted.
River sediments can repeatedly be extracted, that extracts is more abundant, can also carry out to a variety of deposits
Humin is extracted, the humin of extraction is more diversified, analyzes separate sources different structure humin, is conducive to Hu Min
Element is fixed on the research on graphite electrode as electron mediator.The humin obtained after being extracted by aqueous slkali is thick Hu Min
Element can be further processed it, obtain being acylated humin, after acylation processing, be acylated humin in graphite electrode
On fixed effect it is more preferable, it is more efficient by anodizing or reduction.
Preferably, further include the steps that humin is carried out to be acylated processing.
Inventor has found to contain more nitrogen in humin, has amido, processing can be acylated to it.Specifically
Ground obtains mixed solution after mixing acyl chlorides, acid anhydrides and acetic acid according to a certain percentage, 40~70 DEG C is heated to, by Hu Min
Element is put into mixed solution, shake 12 under conditions of 40~70 DEG C~for 24 hours, and it is centrifugated, abandons supernatant liquor, and freeze
It is dried to obtain acylation humin.
Preferably: the volume ratio of acyl chlorides, acid anhydrides and acetic acid is followed successively by (2~4): (3~5): 1, acetic acid is that volume fraction is
The acylation effect of 50% acetic acid, humin is more preferable.
(2), the conducting resinl for adhering to humus and the graphite electrode for smearing conducting resinl are placed into 8~12h at room temperature, made
Humus (humin or being acylated humin) is stably fixed at the surface of conducting resinl on graphite electrode, humus when avoiding being electrolysed
(humin or being acylated humin) enters in electrolyte and cannot be well fixed on graphite electrode, preferably by electrode
Oxidation or reduction.
(3), the graphite electrode for adhering to humus and Ag/AgCl saturation electrode are placed in the cathode chamber containing catholyte
It is interior, platinum electrode is placed in the anode chamber containing anolyte, cathode chamber and anode chamber are carried out by cation-exchange membrane
Separate.
Using graphite electrode as working electrode, Ag/AgCl is saturated electrode as reference electrode, and platinum electrode is used as to electricity
Pole constitutes dual chamber three-electrode system, can restore to fixed humus on the electrode.
Catholyte includes microorganism and halogenated aromatic compound, it is preferable that catholyte includes inorganic salts training
Supporting base, formates, vitamin, microorganism and halogenated aromatic compound, anolyte includes minimal medium.More preferably
Ground, minimal medium include the NH that mass concentration is 1.0~1.5g/L4The CaCl of Cl, 0.04~0.08g/L2·2H2O、
The MgCl of 0.08~0.12g/L2·6H2O, the K of 0.4~0.8g/L2HPO4, 1~3ml/L microelement SL-10 solution, 1
The Se/W solution and 15~20ml/L MOPS buffer of~3ml/L (pH is 7.0~7.2).So that microorganism is grown.
In the present invention, microorganism includes dehalogenation bacillus, bacteroid, sulphur monad and desulfovibrio.These types of microorganism
Be conducive to receive electronics from fixed humin and to halogenated aromatic compound reductive dehalogenation.
Preferably, microorganism is counted according to quantity part, including 2~3 parts of dehalogenation bacillus, 1~2 part of bacteroid, sulphur monad 3
~4 parts and 2~3 parts of desulfovibrio, the various microorganisms under this quantity part are mixed, and halogenated aromatic can be further increased
The effect of the reductive dehalogenation of compound.
(4), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum electrode, constitute three electrode of dual chamber
System is persistently powered to the external voltage that working electrode imposes -600~-700mV 7~9 days.
Apply negative voltage, solid-state humus (humin or being acylated humin) can be restored, by solid-state humus (Hu Min
Element is acylated humin) it is fixed on graphite electrode, restoring solid-state humus by graphite electrode, (humin is acylated recklessly
Quick element), microorganism promotes halogenated using the solid-state humus (humin or being acylated humin) after reduction as electron donor
The reductive dehalogenation of aromatic compound.
Embodiment 1
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps: (1), by conducting resinl being applied to the surface of graphite electrode, and humus is adhered to the surface of conducting resinl.(2), will
The graphite electrode and Ag/AgCl saturation electrode for adhering to humus are placed in the cathode chamber containing catholyte, by platinum electrode
It is placed in the anode chamber containing anolyte, cathode chamber and anode chamber are separated by cation-exchange membrane.Wherein, cathode
Electrolyte includes microorganism and halogenated aromatic compound;Anolyte includes minimal medium.(3), electrochemical operation
It stands connection graphite electrode, Ag/AgCl saturation electrode and platinum electrode, constitutes dual chamber three-electrode system, working electrode is imposed-
The external voltage of 600~-700mV is persistently powered 7 days.
Embodiment 2
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps: (1), by silver conductive adhesive being applied to the surface of graphite electrode, and humin is adhered to the surface of silver conductive adhesive;Its
In, the mass ratio of humin and silver conductive adhesive is 1:10.(2), the silver conductive adhesive and smearing silver conductive adhesive of humin will be adhered to
Graphite electrode place 8h at room temperature.(3), by the graphite electrode for adhering to humus and Ag/AgCl saturation electrode be placed in containing
In the cathode chamber of catholyte, platinum electrode is placed in the anode chamber containing anolyte, cathode chamber and anode chamber are logical
Cation-exchange membrane is crossed to be separated.Wherein, catholyte includes microorganism and halogenated aromatic compound, anolyte
Including minimal medium.(4), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum electrode, are constituted
Dual chamber three-electrode system is persistently powered to the external voltage that working electrode imposes -600~-700mV 9 days.
Embodiment 3
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps: (1) river sediments that in right amount dry partial size be 50 mesh are weighed, in logical nitrogen after mixing with sodium hydroxide solution
6h is shaken in the case where gas, and is centrifugated, supernatant and bottom sand are cast out, middle layer is taken to glue shape deposit, and is freezed dry
It is dry to obtain humin.(2), it is mixed after mixing acyl chlorides, acid anhydrides and acetic acid according to the ratio that volume ratio is followed successively by 2:3:1
Solution is heated to 40 DEG C, humin is put into mixed solution, 12h is shaken under conditions of 40 DEG C, and be centrifugated, in abandoning
Layer clear liquid, and be freeze-dried and obtain being acylated humin.(3), carbonaceous conductive glue is applied to the surface of graphite electrode, and by acyl group
Change the surface that humin is adhered to carbonaceous conductive glue, wherein the mass ratio for being acylated humin and carbonaceous conductive glue is 1:15.(4), will
The graphite electrode of carbonaceous conductive glue and smearing carbonaceous conductive glue that adherency is acylated humin places 8h at room temperature.It (5), will adherency
Graphite electrode and Ag/AgCl the saturation electrode of humus are placed in the cathode chamber containing catholyte, and platinum electrode is placed in
In anode chamber containing anolyte, cathode chamber and anode chamber are separated by cation-exchange membrane;Wherein, catholyte
Liquid includes minimal medium, formates, vitamin, halogenated aromatic compound and microorganism, and anolyte includes inorganic
Salt culture medium;Minimal medium includes the NH that mass concentration is 1.0g/L4The CaCl of Cl, 0.04g/L2·2H2O、0.08g/L
MgCl2·6H2O, the K of 0.4g/L2HPO4, the microelement SL-10 solution of 1ml/L, 1ml/L Se/W solution and 15ml/
L MOPS buffer (pH 7.0).(6), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum electrode,
Dual chamber three-electrode system is constituted, is persistently powered 8 days to the external voltage that working electrode imposes -600~-700mV.
Embodiment 4
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps: (1) river sediments that in right amount dry partial size be 200 mesh are weighed, in logical nitrogen after mixing with sodium hydroxide solution
8h is shaken in the case where gas, and is centrifugated, supernatant and bottom sand are cast out, middle layer is taken to glue shape deposit, and is freezed dry
It is dry to obtain humin.(2), it is mixed after mixing acyl chlorides, acid anhydrides and acetic acid according to the ratio that volume ratio is followed successively by 4:5:1
Solution is heated to 70 DEG C, humin is put into mixed solution, shakes for 24 hours under conditions of 70 DEG C, and be centrifugated, in abandoning
Layer clear liquid, and be freeze-dried and obtain being acylated humin.(3), carbonaceous conductive glue is applied to the surface of graphite electrode, and by acyl group
Change the surface that humin is adhered to carbonaceous conductive glue, wherein the mass ratio for being acylated humin and carbonaceous conductive glue is 1:12.(4), will
The graphite electrode of carbonaceous conductive glue and smearing carbonaceous conductive glue that adherency is acylated humin places 12h at room temperature.(5), it will glue
Graphite electrode and Ag/AgCl the saturation electrode of attached humus are placed in the cathode chamber containing catholyte, and platinum electrode is set
In in the anode chamber containing anolyte, cathode chamber and anode chamber are separated by cation-exchange membrane;Wherein, in cathode
Electrolyte includes minimal medium, formates, vitamin, halogenated aromatic compound and microorganism, electrolyte packet in anode
Include minimal medium;Minimal medium includes the NH that mass concentration is 1.5g/L4The CaCl of Cl, 0.08g/L2·2H2O、
The MgCl of 0.12g/L2·6H2O, the K of 0.8g/L2HPO4, the microelement SL-10 solution of 3ml/L, 3ml/L Se/W solution
With 20ml/L MOPS buffer (pH 7.2).(6), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum
Gold electrode constitutes dual chamber three-electrode system, is persistently powered 7.5 days to the external voltage that working electrode imposes -600~-700mV.
Embodiment 5
A kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, including
Following steps: (1) river sediments that in right amount dry partial size be 100 mesh are weighed, in logical nitrogen after mixing with sodium hydroxide solution
7h is shaken in the case where gas, and is centrifugated, supernatant and bottom sand are cast out, middle layer is taken to glue shape deposit, and is freezed dry
It is dry to obtain humin.(2), it is mixed after mixing acyl chlorides, acid anhydrides and acetic acid according to the ratio that volume ratio is followed successively by 3:4:1
Solution is heated to 60 DEG C, humin is put into mixed solution, 20h is shaken under conditions of 50 DEG C, and be centrifugated, in abandoning
Layer clear liquid, and be freeze-dried and obtain being acylated humin.(3), silver conductive adhesive is applied to the surface of graphite electrode, and by acyl group
Change the surface that humin is adhered to silver conductive adhesive, wherein the mass ratio for being acylated humin and silver conductive adhesive is 1:15.(4), will
The graphite electrode of silver conductive adhesive and smearing silver conductive adhesive that adherency is acylated humin places 10h at room temperature.(5), it will glue
Graphite electrode and Ag/AgCl the saturation electrode of attached humus are placed in the cathode chamber containing catholyte, and platinum electrode is set
In in the anode chamber containing anolyte, double compartment is separated by cation-exchange membrane;Wherein, anaerobism Hu Min in cathode
Plain culture medium includes minimal medium, formates, vitamin, halogenated aromatic compound and microorganism, includes nothing in anode
Machine salt culture medium;Minimal medium includes the NH that mass concentration is 1.2g/L4The CaCl of Cl, 0.05g/L2·2H2O、0.09g/
The MgCl of L2·6H2O, the K of 0.6g/L2HPO4, the microelement SL-10 solution of 2ml/L, the Se/W solution of 2ml/L and
17ml/L MOPS buffer (pH 7.1).(6), electrochemical workstation connection graphite electrode, Ag/AgCl saturation electrode and platinum
Electrode constitutes dual chamber three-electrode system, is persistently powered 8.5 days to the external voltage that working electrode imposes -600~-700mV.
Experimental example
The method of the micro-reduction dehalogenation for the halogenated aromatic pollutant for promoting humus to mediate using electrochemistry is to halogen
Reductive dehalogenation is carried out for aromatic compound, wherein other reaction conditions are identical, fix respectively recklessly on the conducting resinl of graphite electrode
Quick element is acylated humin and blank control (no humin or being acylated humin) progress one Zhou Yihou of reductive dehalogenation, inspection
The case where surveying halogenated aromatic compound reductive dehalogenation in electro-chemical systems catholyte such as table 1:
The case where 1 halogenated aromatic pollutant reductive dehalogenation of table
As it can be seen from table 1 dirty by using the halogenated aromatic that electrochemistry provided by the invention promotes humus to mediate
Contaminate the method for the micro-reduction dehalogenation of object, wherein fix humin respectively on the conducting resinl of graphite electrode and be acylated recklessly
Quick element, can promote microorganism to carry out reductive dehalogenation to halogenated aromatic compound, and microorganism utilizes the Hu after electrode reduction
Quick element or acylation humin can promote to go back the halogenated aromatic compound in catholyte as electron donor
Former dehalogenation.Wherein, for microorganism using humin is acylated as electron donor, reductive dehalogenation effect is more preferable, is good for the environment
Research.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of method of the micro-reduction dehalogenation for the halogenated aromatic pollutant that electrochemistry promotes humus to mediate, feature
It is, includes the following steps:
(1), conducting resinl is applied to the surface of graphite electrode, and humus is adhered to the surface of the conducting resinl;
(2), the graphite electrode for adhering to humus and Ag/AgCl saturation electrode are placed in the cathode chamber containing catholyte,
Platinum electrode is placed in the anode chamber containing anolyte, the cathode chamber and the anode chamber pass through cation-exchange membrane
It is separated;
(3), electrochemical workstation connects the graphite electrode, Ag/AgCl saturation electrode and the platinum electrode, constitutes double
Room three-electrode system is persistently powered to the external voltage that working electrode imposes -600~-700mV 7~9 days;
Wherein, the catholyte includes microorganism and halogenated aromatic compound;The anolyte includes inorganic salts
Culture medium;
The humus is humin, and the humin is to be acylated humin, the preparation method packet for being acylated humin
It includes: obtaining mixed solution after acyl chlorides, acid anhydrides and acetic acid are mixed, be heated to 40~70 DEG C, humin is put into mixed solution
In, shake 12 under conditions of 40~70 DEG C~for 24 hours, and it is centrifugated, abandons supernatant liquor, and is freeze-dried and obtains being acylated recklessly
Quick element.
2. the method according to claim 1, wherein the catholyte further includes minimal medium, first
Hydrochlorate and vitamin.
3. according to the method described in claim 2, it is characterized in that, the minimal medium include mass concentration be 1.0~
The NH of 1.5g/L4The CaCl of Cl, 0.04~0.08g/L2·2H2O, the MgCl of 0.08~0.12g/L2·6H2O, 0.4~0.8g/L
K2HPO4。
4. according to the method described in claim 3, it is characterized in that, the minimal medium further includes the micro of 1~3ml/L
Element S L-10 solution, the Se/W solution of 1~3ml/L and 15~20ml/L MOPS buffer.
5. the method according to claim 1, wherein the microorganism includes dehalogenation bacillus, bacteroid, sulphur list
Born of the same parents bacterium and desulfovibrio.
6. according to the method described in claim 5, it is characterized in that, the microorganism is according to quantity part meter, including dehalogenation bacillus 2
~3 parts, 1~2 part of bacteroid, 3~4 parts of sulphur monad and 2~3 parts of desulfovibrio.
7. the method according to claim 1, wherein the conducting resinl is silver conductive adhesive or carbonaceous conductive glue.
8. the method according to claim 1, wherein the mass ratio for being acylated humin and the conducting resinl
For 1:(10~15).
9. the method according to claim 1, wherein in the step (1), before the step (2), further include by
The step of conducting resinl for adhering to the acylation humin and the graphite electrode for smearing conducting resinl place 8~12h at room temperature.
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WO2001081272A1 (en) * | 2000-04-24 | 2001-11-01 | Alexandr Ivanovich Shulgin | Method for producing a humin-mineral concentrate and device for carrying out said method |
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