CN105194831A - Method for promoting volatile chlorinated hydrocarbons to reduce and decompose through electrical stimulation - Google Patents
Method for promoting volatile chlorinated hydrocarbons to reduce and decompose through electrical stimulation Download PDFInfo
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Abstract
The invention discloses a method for promoting volatile chlorinated hydrocarbons to reduce and decompose through electrical stimulation, which relates to a method for promoting volatile chlorinated hydrocarbons to degrade, and aims to solve the technical problems that existing methods for reducing anaerobic organisms of volatile chlorinated hydrocarbons are slow in degradation velocity, not complete to decompose and easy to produce poisonous and harmful intermediates. The method for promoting the volatile chlorinated hydrocarbons to reduce and decompose through the electrical stimulation comprises steps: 1 preparation of culture medium; 2 enrichment and reinforcement of functional floras; 3 configuration of anaerobic culture; 4 purification of enriched bacterial liquid; 5 construction and start of a biological electrochemical reactor system; and 6 operation of the biological electrochemical reactor system. The method for promoting the volatile chlorinated hydrocarbons to reduce and decompose through the electrical stimulation is a biological method by utilizing a bioelectrochemistry system to promote microorganisms to reduce volatile chlorinated hydrocarbons by adding voltage stimulation. The method for promoting the volatile chlorinated hydrocarbons to reduce and decompose through the electrical stimulation can achieve degradation rate above 95% in 24h, can reduce pollutants containing the volatile chlorinated hydrocarbons, and is used in environmental management engineering.
Description
Technical field
The present invention relates to the method promoting volatile chlorinated hydrocarbon (VCHs) reduction decomposition.
Technical background
Volatile chlorinated hydrocarbon (VCHs) is the extremely strong persistent organic pollutants of a class harmfulness, there is volatile, the feature such as high toxicity, high density, highly dissoluble, there is the carcinogenic mutagenic risk of teratogenesis, long-term existence constantly can accumulate and cause serious harm to the ecosystem and human health in environment.Along with volatility chlorinated aliphatic hydrocarbon is in the extensive use in the fields such as process hides, dry-cleaning, agricultural chemicals, cause the recall rate of this pollutant in soil and groundwater high, a lot of type VCHs is classified as priority pollutants blacklist by China and U.S.A Environmental Protection Agency at present.
About 2012, the Master's thesis " different materials loaded with nano Zero-valent Iron removes the experimental study of volatile chlorinated hydrocarbon in water/soil " of refined beautiful woman discloses a kind of method removing volatile chlorinated hydrocarbon (VCHs) with inorganic modified native loaded with nano-iron, during result table, in aqueous, the removal effect of inorganic modified native loaded with nano-iron to volatile chlorinated hydrocarbon (VCHs) is the highest, can be the trichloro-ethylene (TCE) and 1 of 10mg/L by concentration in 6 hours, 2-dichloroethanes (1,2-DCA) is degraded 76.27% and 44.38%.But this kind of method is difficult to degradable chlorohydrocarbon, and application is vulnerable to that Nanoscale Iron preparation process is complicated, cost is high and reduction process easily forms iron oxide and causes reaction to be difficult to continue restrictions such as carrying out.Microbial decomposition method, as microbiological anaerobic reduction dechlorination process, utilize microorganism self respiratory metabolism degradating chloro hydrocarbon, cost is low, environmental protection, but due to anaerobe (reduction dechlorination bacterium) metabolic rate slow, cause chlorohydrocarbon decomposition rate low, decompose not exclusively and easily produce poisonous and harmful intermediate product, therefore greatly limit the application of biological reducing at engineering field.
Summary of the invention
The present invention will solve the technical problem that the anaerobic organism method of reducing degradation speed of existing volatility chlorinated aliphatic hydrocarbon is slow, decompose not exclusively, easily produce poisonous and harmful intermediate product, and provides a kind of electro photoluminescence to promote the method for volatile chlorinated hydrocarbon anaerobic organism reduction decomposition.
A kind of electro photoluminescence of the present invention promotes that the method that volatile chlorinated hydrocarbon biological reducing decomposes is carried out according to the following steps:
One, the preparation of culture medium: the ratio adding 10 ~ 15mL activated sludge in 50mL distilled water, joins in vial by distilled water and activated sludge, and after nitrogen blowing 15 ~ 20min, sealing, to keep anaerobism in bottle, obtains culture medium;
Two, the enrichment of functional flora, strengthening: join in culture medium by sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, culture medium is placed in 30 DEG C of constant incubators, measured the degraded situation of volatility chlorinated aliphatic hydrocarbon every 3 ~ 5 days; When volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration, again add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, sodium acetate solution is identical with primary addition with the addition of volatility chlorinated aliphatic hydrocarbon, when volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration again, add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again, addition is identical with primary addition, when volatility chlorinated aliphatic hydrocarbon is down to less than 20% of initial incremental amount, complete the enrichment of functional flora, strengthening, obtain enrichment bacterium liquid;
Three, Anaerobic culturel liquid is configured;
Four, purification enrichment bacterium liquid: Anaerobic culturel liquid step 3 obtained adds in vial, seals after the nitrogen 15 ~ 20min that exposes to the sun, then in temperature be 120 ~ 125 DEG C, pressure is the autoclave sterilizing 30 ~ 40min of 100kPa ~ 110kPa, obtains anaerobic culture medium; Enrichment bacterium liquid step 2 obtained is inoculated in anaerobic culture medium, then adds volatility chlorinated aliphatic hydrocarbon; Anaerobic culture medium is placed in 30 ~ 32 DEG C of constant incubators, the degraded situation of volatility chlorinated aliphatic hydrocarbon is measured every 1 ~ 2 day, when volatility chlorinated aliphatic hydrocarbon drops to less than 50% of primary quantity, again add volatility chlorinated aliphatic hydrocarbon, after repeating to add volatility chlorinated aliphatic hydrocarbon 2 ~ 3 times by this rule, obtain first generation culture medium; After first generation culture medium 5 ~ 6 generations of switching, obtain the enrichment bacterium liquid of purifying;
Five, the building and start of bioelectrochemical system reactor: this bioelectrochemical system reactor is made up of anode chamber (1), cathode chamber (2), cation-exchange membrane (3), two carbon brush electrodes (4) and saturated calomel electrode (5), wherein anode chamber (1) and cathode chamber (2) are separated (3) with cation-exchange membrane, two carbon brush electrodes (4) are placed in anode chamber (1) and cathode chamber (2) respectively, and be communicated with external circuit, saturated calomel electrode (5) is inserted in cathode chamber (2), the potassium ferrocyanide solution of 100 ~ 120mM is joined in anode chamber, expose to the sun nitrogen 15 ~ 20 minutes, being 1:(20 ~ 40 by the enrichment bacterium liquid of purifying and the volume ratio of Anaerobic culturel liquid) the enrichment bacterium liquid of purifying that obtains of the Anaerobic culturel liquid step 3 prepared and step 4 joins in cathode chamber (2), sodium acetate solution and volatility chlorinated aliphatic hydrocarbon is added in the same way in cathode chamber (2), by dc source to the moon, sun the two poles of the earth apply voltage, when detecting that volatility chlorinated aliphatic hydrocarbon concentration is down to less than 20% of initial incremental amount, repeat to add the operation 5 ~ 6 times of sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again in cathode chamber, obtain the bio-electrochemical reactor system starting and successfully there is volatility chlorinated aliphatic hydrocarbon reducing power,
Six, the operation of bioelectrochemical system reactor: sodium acetate solution and the pollutant containing volatility chlorinated aliphatic hydrocarbon are joined step 5 and starts in the cathode chamber of successful bio-electrochemical reactor, voltage is applied to yin, yang the two poles of the earth by dc source, after 15 ~ 25 hours, complete the reduction decomposition of volatile chlorinated hydrocarbon biology.
The present invention is that one utilizes bioelectrochemical system (BES) to be stimulated the biological method promoting micro-reduction volatile chlorinated hydrocarbon by applied voltage, volatile chlorinated hydrocarbon comprises tetrachloro-ethylene (PCE), trichloro-ethylene (TCE) and 1,2-dichloroethanes (1,2-DCA).The present invention, on the basis of biological reducing method, by the extra electric field that input is very little, for microorganism provides extra reducing power, stimulates born of the same parents' exoelectron transmission efficiency of microorganism, reaches the object of enhancement microbiological reduction volatilization halogenated aliphatic hydrocarbon.The present invention adopts anaerobic reductive dechlorination flora-cathode catalysis system to promote the reduction decomposition of volatility chlorinated aliphatic hydrocarbon, completes bioelectrochemistry negative electrode and promotes that the reduction decomposition of volatility chlorinated aliphatic hydrocarbon needs two processes: (1) microorganism cultivates domestication by extra electric field; (2) extra electric field stimulates.Biological-cathode is promoted that the degradation efficiency Sum decomposition product of volatility chlorinated aliphatic hydrocarbon carries out quantitative and qualitative analysis, realizes 1,2-DCA, the efficient reduction dechlorination of TCE and PCE, improve product recoveries.The method applied in the present invention can reach more than 95% at the degradation rate of 24h, relative to traditional physics, chemistry, bioremediation, has that degradation efficiency is high, energy consumption is low, a feature of innoxious and non-secondary pollution.A kind of method is provided for solving the pollution problem in the environment of volatility chlorinated aliphatic hydrocarbon.
Accompanying drawing explanation
Bioelectrochemical system structure of reactor schematic diagram described in Fig. 1 detailed description of the invention one; Wherein 1 is anode chamber, and 2 is cathode chamber, and 3 is cation-exchange membrane, and 4 is carbon brush, and 5 is saturated calomel electrode, and 6 is resistance.
Fig. 2 is volatile chlorinated hydrocarbon pollutant levels relation curve over time in test one.
Detailed description of the invention
Detailed description of the invention one: a kind of electro photoluminescence of present embodiment promotes that the method that volatile chlorinated hydrocarbon biological reducing decomposes is carried out according to the following steps:
One, the preparation of culture medium: the ratio adding 10 ~ 15mL activated sludge in 50mL distilled water, joins in vial by distilled water and activated sludge, and after nitrogen blowing 15 ~ 20min, sealing, to keep anaerobism in bottle, obtains culture medium;
Two, the enrichment of functional flora, strengthening: join in culture medium by sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, culture medium is placed in 30 DEG C of constant incubators, measured the degraded situation of volatility chlorinated aliphatic hydrocarbon every 3 ~ 5 days; When volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration, again add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, sodium acetate solution is identical with primary addition with the addition of volatility chlorinated aliphatic hydrocarbon, when volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration again, add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again, addition is identical with primary addition, when volatility chlorinated aliphatic hydrocarbon is down to less than 20% of initial incremental amount, complete the enrichment of functional flora, strengthening, obtain enrichment bacterium liquid;
Three, Anaerobic culturel liquid is configured;
Four, purification enrichment bacterium liquid: Anaerobic culturel liquid step 3 obtained adds in vial, seals after the nitrogen 15 ~ 20min that exposes to the sun, then in temperature be 120 ~ 125 DEG C, pressure is the autoclave sterilizing 30 ~ 40min of 100kPa ~ 110kPa, obtains anaerobic culture medium; Enrichment bacterium liquid step 2 obtained is inoculated in anaerobic culture medium, then adds volatility chlorinated aliphatic hydrocarbon; Anaerobic culture medium is placed in 30 ~ 32 DEG C of constant incubators, the degraded situation of volatility chlorinated aliphatic hydrocarbon is measured every 1 ~ 2 day, when volatility chlorinated aliphatic hydrocarbon drops to less than 50% of primary quantity, again add volatility chlorinated aliphatic hydrocarbon, after repeating to add volatility chlorinated aliphatic hydrocarbon 2 ~ 3 times by this rule, obtain first generation culture medium; After first generation culture medium 5 ~ 6 generations of switching, obtain the enrichment bacterium liquid of purifying;
Five, the building and start of bioelectrochemical system reactor: this bioelectrochemical system reactor is made up of anode chamber 1, cathode chamber 2, cation-exchange membrane 3, two carbon brush electrodes 4 and saturated calomel electrode 5, wherein anode chamber 1 and cathode chamber 2 separate 3 with cation-exchange membrane, two carbon brush electrodes 4 are placed in anode chamber 1 and cathode chamber 2 respectively, and be communicated with external circuit, saturated calomel electrode 5 is inserted in cathode chamber 2, the potassium ferrocyanide solution of 100 ~ 120mM is joined in anode chamber, expose to the sun nitrogen 15 ~ 20 minutes, being 1:(20 ~ 40 by the enrichment bacterium liquid of purifying and the volume ratio of Anaerobic culturel liquid) the enrichment bacterium liquid of purifying that obtains of the Anaerobic culturel liquid step 3 prepared and step 4 joins in cathode chamber 2, sodium acetate solution and volatility chlorinated aliphatic hydrocarbon is added in the same way in cathode chamber 2, by dc source to the moon, sun the two poles of the earth apply voltage, when detecting that volatility chlorinated aliphatic hydrocarbon concentration is down to less than 20% of initial incremental amount, repeat to add the operation 5 ~ 6 times of sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again in cathode chamber, obtain the bio-electrochemical reactor system starting and successfully there is volatility chlorinated aliphatic hydrocarbon reducing power,
Six, the operation of bioelectrochemical system reactor: sodium acetate solution and the pollutant containing volatility chlorinated aliphatic hydrocarbon are joined step 5 and starts in the cathode chamber of successful bio-electrochemical reactor, voltage is applied to yin, yang the two poles of the earth by dc source, after 15 ~ 25 hours, complete the reduction decomposition of volatile chlorinated hydrocarbon biology.
Detailed description of the invention two: present embodiment and detailed description of the invention one are trichloro-ethylene, tetrachloro-ethylene or 1,2-dichloroethanes unlike volatility chlorinated aliphatic hydrocarbon in step 2; Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two are composed as follows unlike: the Anaerobic culturel liquid described in step 3: the proportions comprising following constituent by every 1000mL Anaerobic culturel liquid: 11.55gNa
2hPO
412H
2o, 2.77gNaH
2pO
42H
2o, 0.31gNH
4cl, 0.13gKCl, 0.41gCH
3the distilled water of COONa, 0.1mL vitamin liquid, 0.1mL mineral element liquid and surplus; Wherein said vitamin liquid is every 1000mL vitamin liquid containing the distilled water of 2.0mg biotin, 2.0mg folic acid, 10.0mg puridoxine hydrochloride, 5.0mg thiamine, 5.0mg riboflavin, 5.0mg nicotinic acid, 5.0mgD-calcium pantothenate, 0.1mg vitamin B12,5.0mg p-aminobenzoic acid, 5.0mg lipoic acid and surplus; Described mineral element liquid is that every 1000mL mineral element liquid is containing 1.5g NTA, 3.0gMgSO
47H
2o, 0.5gMnSO
4h
2o, 1.0gNaCl, 0.1gFeSO
47H
2o, 0.1gCoCl
26H
2o, 0.1gCaCl
2, 0.1gZnSO
47H
2o, 0.01gCuSO
45H
2o, 0.01gAlK (SO
4)
212H
2o, 0.01gH
3bO
3, 0.01gNa
2moO
42H
2the distilled water of O and surplus; Other is identical with embodiment one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the concentration of the sodium acetate described in step 2 is 10 ~ 12mmol/L, the concentration of volatility chlorinated aliphatic hydrocarbon is 2.0 ~ 2.2mmol/L; Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: enrichment bacterium liquid is inoculated in anaerobic culture medium unlike first time in step 4 by one of present embodiment and detailed description of the invention one to four, is 10 by clump count in anaerobic culture medium
7-10
8cells/mL adds; Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five add volatility chlorinated aliphatic hydrocarbon unlike first time in step 4 in anaerobic culture medium, are that 2.0 ~ 2.2mmol/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon; Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six are unlike in step 4, and second time adds volatility chlorinated aliphatic hydrocarbon in anaerobic culture medium, is that 2.0 ~ 2.2mmol/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon; Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven, unlike in step 5, add sodium acetate solution in cathode chamber is that 10mmol/L adds by the concentration of sodium acetate; When adding volatility chlorinated aliphatic hydrocarbon, be that 0.5-2.0mmoles/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon; Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight are unlike in step 6, and the concentration of sodium acetate is 10mmol/L; Other is identical with one of detailed description of the invention one to eight.
With following case verification beneficial effect of the present invention:
Test one: a kind of electro photoluminescence of this test promotes that the method that volatility chlorinated aliphatic hydrocarbon biological reducing decomposes is carried out according to the following steps:
One, the preparation of culture medium: activated sludge 50mL distilled water and 10mL being taken from municipal sewage plant is added in the thin mouth medicine bottle of 120mL, after nitrogen blowing 15min, add polytetrafluoroethylene (PTFE) plug and aluminum foil cover sealing, to keep anaerobic environment in bottle, obtain culture medium;
Two, the enrichment of functional flora, strengthening: get three groups of parallelly cultivate bases and weave into No. 1, No. 2 and No. 3, often adding 0.3mL molar concentration in group culture medium is that the aqueous sodium acetate solution of 1mol/L is as electron donor, 20uL1 is added in No. 1 culture medium, 2-dichloroethanes (1,2-DCA), 10uL trichloro-ethylene (TCE) is added in No. 2 culture mediums, 10uL tetrachloro-ethylene (PCE) is added in No. 3 culture mediums, 1,2-dichloroethanes, trichloro-ethylene and tetrachloro-ethylene are as target contaminant--volatility chlorinated aliphatic hydrocarbon; Three groups of culture mediums are all placed in 30 DEG C of constant incubators, measure the degraded situation of volatility chlorinated aliphatic hydrocarbon every 3 days; When volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration, again add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, addition is identical with primary addition, when volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration; Add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again, addition is identical with primary addition, when volatility chlorinated aliphatic hydrocarbon is down to less than 20% of initial incremental amount, completes the enrichment of functional flora, strengthening, obtains enrichment bacterium liquid;
Three, Anaerobic culturel liquid is configured: to be made up of following constituent by every 1000mL Anaerobic culturel liquid and to prepare: 11.55gNa
2hPO
412H
2o, 2.77gNaH
2pO
42H
2o, 0.31gNH
4cl, 0.13gKCl, 0.41gCH
3the distilled water of COONa, 0.1mL vitamin liquid, 0.1mL mineral element liquid and surplus; Wherein said vitamin liquid is every 1000mL vitamin liquid containing the distilled water of 2.0mg biotin, 2.0mg folic acid, 10.0mg puridoxine hydrochloride, 5.0mg thiamine, 5.0mg riboflavin, 5.0mg nicotinic acid, 5.0mgD-calcium pantothenate, 0.1mg vitamin B12,5.0mg p-aminobenzoic acid, 5.0mg lipoic acid and surplus; Described mineral element liquid is that every 1000mL mineral element liquid is containing 1.5g NTA, 3.0gMgSO
47H
2o, 0.5gMnSO
4h
2o, 1.0gNaCl, 0.1gFeSO
47H
2o, 0.1gCoCl
26H
2o, 0.1gCaCl
2, 0.1gZnSO
47H
2o, 0.01gCuSO
45H
2o, 0.01gAlK (SO
4)
212H
2the distilled water of O, 0.01gH3BO3,0.01gNa2MoO42H2O and surplus, obtains Anaerobic culturel liquid;
Four, purification enrichment bacterium liquid: Anaerobic culturel liquid 60mL step 3 obtained adds in the thin mouth vial of 120mL, fill three bottles, label is I, II and No. III respectively, expose to the sun after nitrogen 15min and seal, again in 121 DEG C, pressure is the autoclave sterilization pot sterilizing 30min of 100KPa, obtains anaerobic culture medium; No. 1 that 6mL step 2 is obtained rich bacterium liquid is inoculated in No. I anaerobic culture medium, and adds 20uL1,2-dichloroethanes (1,2-DCA); No. 2 that 6mL step 2 are obtained rich bacterium liquid are inoculated in No. II anaerobic culture medium, and add 10uL trichloro-ethylene (TCE); No. 3 that 6mL step 2 are obtained rich bacterium liquid are inoculated in No. III anaerobic culture medium, and add 10uL tetrachloro-ethylene (PCE); I, II and No. III anaerobic culture medium is placed in 30 DEG C of constant incubators, the degraded situation of volatility chlorinated aliphatic hydrocarbon is measured every 1 day, when volatility chlorinated aliphatic hydrocarbon concentration drops to less than 50% of primary quantity, add again and add the volatility chlorinated aliphatic hydrocarbon of equivalent with kind respectively, after repeating 3 times, obtain first generation culture medium; After first generation culture medium 5 ~ 6 generations of switching, obtain the enrichment bacterium liquid of the enrichment bacterium liquid of 1,2-dichloroethanes purifying, the enrichment bacterium liquid of trichloro-ethylene purifying and tetrachloro-ethylene purifying respectively;
Five, build and start three cover bioelectrochemical system reactors: this bioelectrochemical system reactor is made up of anode chamber 1, cathode chamber 2, cation-exchange membrane 3, two carbon brush electrodes 4 and saturated calomel electrode 5, wherein anode chamber and cathode chamber are separated with cation-exchange membrane, two carbon brush electrodes are placed in anode chamber and cathode chamber respectively, and be connected with the resistance 6 of external circuit by 10 ohm, saturated calomel electrode 5 is inserted in cathode chamber 2; 2. number and 3. join in anode chamber by the potassium ferrocyanide solution of 100mmoles/L, expose to the sun nitrogen 15 minutes, and now 1. number, a number bio-electrochemical reactor has been built respectively.The enrichment bacterium liquid of the purifying that Anaerobic culturel liquid step 3 obtained again and step 4 obtain is by volume for the ratio of 5:2 is linked in cathode chamber, voltage (regulating and maintaining each reactor negative electrode relative standard hydrogen electrode current potential is-0.26V) is applied to yin, yang the two poles of the earth by dc source, the resistance of 10 ohm that connect in circuit is current sampling resistor, calculates by the voltage at measuring resistance two ends the electric current flowing through circuit.Add sodium acetate solution and 20uL1 that 0.3mL molar concentration is 1mol/L afterwards respectively, 2-DCA, 1. number 10uLTCE and 10uLPCE is to, 2. number and 3. number reactor cathod system, when detecting that volatility chlorinated aliphatic hydrocarbon is down to less than 20% of initial incremental amount, repeating above operation 5 times, succeeding start 1, the bio-electrochemical reactor of 2-DCA, TCE and PCE;
Six, by dc source to the moon, sun the two poles of the earth apply voltage, regulate each reactor negative electrode relative standard hydrogen electrode current potential for-0.26V is as working electrode, reactor negative electrode adds the sodium acetate solution and volatility chlorinated aliphatic hydrocarbon that 0.3mL molar concentration is 1mol/L, the voltage at current sampling resistor two ends and cathode potential are measured and real time record 0h by data logger, 2h, 5h, 8h, 12h, 24h, the reduction decomposition situation of the 28 little biologies of volatile chlorinated hydrocarbon constantly, relation curve is as shown in Figure 2 over time for the content of the three kinds of volatility volatility chlorinated aliphatic hydrocarbons obtained.As can be seen from Figure 2, at the bioelectrochemical system reactor of this test in the operation phase, the content of three kinds of volatility chlorinated aliphatic hydrocarbons all can reach more than 95% at the degradation rate of 24h, the reduction decomposition of volatile chlorinated hydrocarbon biology is relatively more complete, and produces without poisonous and harmful intermediate product in course of reaction.
Claims (9)
1. electro photoluminescence promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes to it is characterized in that the method is carried out according to the following steps:
One, the preparation of culture medium: the ratio adding 10 ~ 15mL activated sludge in 50mL distilled water, joins in vial by distilled water and activated sludge, and after nitrogen blowing 15 ~ 20min, sealing, to keep anaerobism in bottle, obtains culture medium;
Two, the enrichment of functional flora, strengthening: join in culture medium by sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, culture medium is placed in 30 DEG C of constant incubators, measured the degraded situation of volatility chlorinated aliphatic hydrocarbon every 3 ~ 5 days; When volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration, again add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon, sodium acetate solution is identical with primary addition with the addition of volatility chlorinated aliphatic hydrocarbon, when volatility chloro fat hydrocarbon content is down to less than 50% of initial concentration again, add sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again, addition is identical with primary addition, when volatility chlorinated aliphatic hydrocarbon is down to less than 20% of initial incremental amount, complete the enrichment of functional flora, strengthening, obtain enrichment bacterium liquid;
Three, Anaerobic culturel liquid is configured;
Four, purification enrichment bacterium liquid: Anaerobic culturel liquid step 3 obtained adds in vial, seals after the nitrogen 15 ~ 20min that exposes to the sun, then in temperature be 120 ~ 125 DEG C, pressure is the autoclave sterilizing 30 ~ 40min of 100kPa ~ 110kPa, obtains anaerobic culture medium; Enrichment bacterium liquid step 2 obtained is inoculated in anaerobic culture medium, then adds volatility chlorinated aliphatic hydrocarbon; Anaerobic culture medium is placed in 30 ~ 32 DEG C of constant incubators, the degraded situation of volatility chlorinated aliphatic hydrocarbon is measured every 1 ~ 2 day, when volatility chlorinated aliphatic hydrocarbon drops to less than 50% of primary quantity, again add volatility chlorinated aliphatic hydrocarbon, after repeating to add volatility chlorinated aliphatic hydrocarbon 2 ~ 3 times by this rule, obtain first generation culture medium; After first generation culture medium 5 ~ 6 generations of switching, obtain the enrichment bacterium liquid of purifying;
Five, the building and start of bioelectrochemical system reactor: this bioelectrochemical system reactor is made up of anode chamber (1), cathode chamber (2), cation-exchange membrane (3), two carbon brush electrodes (4) and saturated calomel electrode (5), wherein anode chamber (1) and cathode chamber (2) are separated (3) with cation-exchange membrane, two carbon brush electrodes (4) are placed in anode chamber (1) and cathode chamber (2) respectively, and be communicated with external circuit, saturated calomel electrode (5) is inserted in cathode chamber (2), the potassium ferrocyanide solution of 100 ~ 120mM is joined in anode chamber, expose to the sun nitrogen 15 ~ 20 minutes, being 1:(20 ~ 40 by the enrichment bacterium liquid of purifying and the volume ratio of Anaerobic culturel liquid) the enrichment bacterium liquid of purifying that obtains of the Anaerobic culturel liquid step 3 prepared and step 4 joins in cathode chamber (2), sodium acetate solution and volatility chlorinated aliphatic hydrocarbon is added in the same way in cathode chamber (2), by dc source to the moon, sun the two poles of the earth apply voltage, when detecting that volatility chlorinated aliphatic hydrocarbon concentration is down to less than 20% of initial incremental amount, repeat to add the operation 5 ~ 6 times of sodium acetate solution and volatility chlorinated aliphatic hydrocarbon again in cathode chamber, obtain the bio-electrochemical reactor system starting and successfully there is volatility chlorinated aliphatic hydrocarbon reducing power,
Six, the operation of bioelectrochemical system reactor: sodium acetate solution and the pollutant containing volatility chlorinated aliphatic hydrocarbon are joined step 5 and starts in the cathode chamber (2) of successful bio-electrochemical reactor, voltage is applied to yin, yang the two poles of the earth by dc source, after 15 ~ 25 hours, complete the reduction decomposition of volatile chlorinated hydrocarbon biology.
2. a kind of electro photoluminescence according to claim 1 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes to it is characterized in that in step 2, volatility chlorinated aliphatic hydrocarbon is trichloro-ethylene, tetrachloro-ethylene or 1,2-dichloroethanes.
3. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes to it is characterized in that the composed as follows of the Anaerobic culturel liquid described in step 3: the proportions comprising following constituent by every 1000mL Anaerobic culturel liquid: 11.55gNa
2hPO
412H
2o, 2.77gNaH
2pO
42H
2o, 0.31gNH
4cl, 0.13gKCl, 0.41gCH
3the distilled water of COONa, 0.1mL vitamin liquid, 0.1mL mineral element liquid and surplus; Wherein said vitamin liquid is every 1000mL vitamin liquid containing the distilled water of 2.0mg biotin, 2.0mg folic acid, 10.0mg puridoxine hydrochloride, 5.0mg thiamine, 5.0mg riboflavin, 5.0mg nicotinic acid, 5.0mgD-calcium pantothenate, 0.1mg vitamin B12,5.0mg p-aminobenzoic acid, 5.0mg lipoic acid and surplus; Described mineral element liquid is that every 1000mL mineral element liquid is containing 1.5g NTA, 3.0gMgSO
47H
2o, 0.5gMnSO
4h
2o, 1.0gNaCl, 0.1gFeSO
47H
2o, 0.1gCoCl
26H
2o, 0.1gCaCl
2, 0.1gZnSO
47H
2o, 0.01gCuSO
45H
2o, 0.01gAlK (SO
4)
212H
2o, 0.01gH
3bO
3, 0.01gNa
2moO
42H
2the distilled water of O and surplus.
4. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes to it is characterized in that the concentration of the sodium acetate described in step 2 is 10 ~ 12mmol/L, the concentration of volatility chlorinated aliphatic hydrocarbon is 2.0 ~ 2.2mmol/L.
5. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes, and it is characterized in that in step 4, enrichment bacterium liquid is inoculated in anaerobic culture medium by first time, is 10 by clump count in anaerobic culture medium
7-10
8cells/mL adds.
6. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes, it is characterized in that in step 4, first time adds volatility chlorinated aliphatic hydrocarbon in anaerobic culture medium, is that 2.0 ~ 2.2mmol/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon.
7. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes, it is characterized in that in step 4, second time adds volatility chlorinated aliphatic hydrocarbon in anaerobic culture medium, is that 2.0 ~ 2.2mmol/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon.
8. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes, and it is characterized in that, in step 5, adding sodium acetate solution in cathode chamber, is that 10mmol/L adds by the concentration of sodium acetate; Adding volatility chlorinated aliphatic hydrocarbon, is that 0.5-2.0mmol/L adds by the concentration of volatility chlorinated aliphatic hydrocarbon.
9. a kind of electro photoluminescence according to claim 1 and 2 promotes the method that volatile chlorinated hydrocarbon biological reducing decomposes, and it is characterized in that in step 6, the concentration of sodium acetate is 10mmol/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI684575B (en) * | 2018-11-15 | 2020-02-11 | 國立中興大學 | Screening method for decomposing microbial flora in the polluted site, and rapid decomposition method for pollutants in the local |
| CN113003703A (en) * | 2021-03-16 | 2021-06-22 | 南京理工大学 | Device and method for treating nitrogen-containing heterocyclic compound wastewater |
| CN114524505A (en) * | 2022-01-28 | 2022-05-24 | 哈尔滨工业大学 | Method for accurately and completely dechlorinating chlorohydrocarbon based on slow-release carbon source coupling bioelectrochemical system |
| CN115487661A (en) * | 2022-10-09 | 2022-12-20 | 浙江工业大学 | Method for degrading 1, 2-dichloroethane by using photoelectricity-driven microbial photoelectrolysis cell |
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| CN1195373A (en) * | 1996-04-22 | 1998-10-07 | 丰田自动车株式会社 | Microorganisms that decompose halogenated hydrocarbons and their use |
| CN102321659A (en) * | 2011-08-30 | 2012-01-18 | 浙江工业大学 | Chlorinated aliphatic hydrocarbon degradative plasmid pRC11, engineered bacteria and application thereof |
| CN102533619A (en) * | 2012-02-29 | 2012-07-04 | 华东理工大学 | Preparation method of hydrochloric ether efficient aerobic degradation mixed bacteria and application thereof |
| CN102816696A (en) * | 2012-07-06 | 2012-12-12 | 华东理工大学 | Preparation method of fungicide for anaerobic degradation of hydrochloric ether and application thereof |
| CN103992013A (en) * | 2014-06-09 | 2014-08-20 | 江苏德鑫环保科技有限公司 | Method and equipment for treating high-concentration refractory chemical wastewater |
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| CN1195373A (en) * | 1996-04-22 | 1998-10-07 | 丰田自动车株式会社 | Microorganisms that decompose halogenated hydrocarbons and their use |
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| CN102816696A (en) * | 2012-07-06 | 2012-12-12 | 华东理工大学 | Preparation method of fungicide for anaerobic degradation of hydrochloric ether and application thereof |
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| TWI684575B (en) * | 2018-11-15 | 2020-02-11 | 國立中興大學 | Screening method for decomposing microbial flora in the polluted site, and rapid decomposition method for pollutants in the local |
| CN113003703A (en) * | 2021-03-16 | 2021-06-22 | 南京理工大学 | Device and method for treating nitrogen-containing heterocyclic compound wastewater |
| CN114524505A (en) * | 2022-01-28 | 2022-05-24 | 哈尔滨工业大学 | Method for accurately and completely dechlorinating chlorohydrocarbon based on slow-release carbon source coupling bioelectrochemical system |
| CN115487661A (en) * | 2022-10-09 | 2022-12-20 | 浙江工业大学 | Method for degrading 1, 2-dichloroethane by using photoelectricity-driven microbial photoelectrolysis cell |
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