Summary of the invention
The defect existed for prior art, the present invention provides a kind of and uses microbiological fuel cell to carry out water quality
The Apparatus and method for of biological toxicity tests, in order to solve the problems referred to above.
The technical solution used in the present invention is as follows:
The present invention provides a kind of equipment using microbiological fuel cell to carry out water quality biological Toxicity Monitoring, including:
Culture fluid case (3), distilled water tank (2), water sample filter (1), the first sense channel, the second detection are led to
Road and signal processing and display circuit (10);
Wherein, described first sense channel includes the first switching valve (4), the first water sample pump (6), the first training
Nutrient solution pump (5), the first mixing pump (7), the first microbiological fuel cell (8) and the first pre-amplification circuit
(9);First output interface of described water sample filter (1) and the first output of described distilled water tank (2)
Interface is connected respectively to the input interface of described first switching valve (4), and described first switches the defeated of valve (4)
Outgoing interface is connected to the input interface of described first water sample pump (6);The first of described culture fluid case (3) is defeated
Outgoing interface is connected to the described first input interface cultivating liquid pump (5);Described first water sample pump (6) defeated
Outgoing interface and the described first output interface cultivating liquid pump (5) are all connected to described first mixing pump (7)
Input interface, the output interface of described first mixing pump (7) is connected to described first microbiological fuel cell (8)
Input interface, the output interface of described first microbiological fuel cell (8) is by described first preposition amplification
Described signal processing and display circuit (10) it is connected to after circuit (9);
Described second sense channel includes the second switching valve (11), the second water sample pump (13), the second culture fluid
Pump (12), the second mixing pump (14), the second microbiological fuel cell (15) and the second pre-amplification circuit
(16);Second output interface of described water sample filter (1) and the second output of described distilled water tank (2)
Interface is connected respectively to the input interface of described second switching valve (11), described second switching valve (11)
Output interface is connected to the input interface of described second water sample pump (13);The second of described culture fluid case (3)
Output interface is connected to the described second input interface cultivating liquid pump (12);Described second water sample pump (13)
Output interface and described second cultivate liquid pump (12) output interface be all connected to described second mixing pump (14)
Input interface, the output interface of described second mixing pump (14) be connected to described second Microbial fuel electricity
The input interface in pond (15), the output interface of described second microbiological fuel cell (15) is by described the
Described signal processing and display circuit (10) it is connected to after two pre-amplification circuits (16).
Preferably, thermostat (17) is also included;Described first microbiological fuel cell (8), described first
Pre-amplification circuit (9), described second microbiological fuel cell (15) and described second pre-amplification circuit
(16) described thermostat (17) it is respectively positioned on internal.
Preferably, the model that the parts of following group are used is identical:
Described first switching valve (4) and described second switching valve (11);Described first water sample pump (6) and institute
State the second water sample pump (13);Described first cultivates liquid pump (5) and described second cultivates liquid pump (12);Described
First mixing pump (7) and described second mixing pump (14);Described first microbiological fuel cell (8) and institute
State the second microbiological fuel cell (15);Put before described first pre-amplification circuit (9) and described second
Big circuit (16).
Preferably, described first microbiological fuel cell (8) and described second microbiological fuel cell (15)
Structure include respectively: microbiological fuel cell body (51), anode (54), negative electrode (56), water inlet
(52), outlet (53) and separation membrane (55);
Described anode (54) is arranged on the inner chamber of described microbiological fuel cell body (51), by this inner chamber
It is separated to form inner chamber (57) and lower inner cavity (58);The bottom of described lower inner cavity (58) and described water inlet
(52) connection;The circumference of described upper inner chamber (57) is uniformly arranged at least one described outlet (53);Institute
The top stating inner chamber (57) arranges described separation membrane (55), on described separation membrane (55) closely
Fit described negative electrode (56), and, described negative electrode (56) is exposed in air.
Preferably, described water inlet (52) and described outlet (53) all with oxygen impermeable pvc pipe or pump
Pipe is connected.
The present invention also provides for a kind of method using microbiological fuel cell to carry out water quality biological Toxicity Monitoring, bag
Include following steps:
S1, in the case of daily monitoring, the first sense channel enters detected water sample, is used for monitoring detected water sample
Bio-toxicity;Second sense channel enters the distilled water with detected water sample equivalent, as blank;Tool
Body operational circumstances is as follows:
S11: switching the first switching valve (4), makes output interface and the first water sample pump of water sample filter (1)
(6) connection, and the output interface of distilled water tank (2) and the first water sample pump (6) do not connect;Then, quilt
Survey water sample is after water sample filter (1) filters, after the first switching valve (4) and the first water sample pump (6),
Enter the first mixing pump (7);Meanwhile, the culture fluid in culture fluid case (3) is by the first cultivation liquid pump (5)
After also into the first mixing pump (7);In the first mixing pump (7), detected water sample and culture fluid are by a definite proportion
Example mixes, subsequently into the first microbiological fuel cell (8);First microbiological fuel cell (8) exports
The signal of telecommunication is amplified into signal processing and display circuit (10) through the first pre-amplification circuit (9);
Meanwhile, for the second sense channel, switching the second switching valve (11), distilled water tank (2) is made
Output interface and the connection of the second water sample pump (13), and the output interface of water sample filter (1) and the second water
Sample pump (13) does not connects;Then, distilled water is by the second switching valve (11) and the second water sample pump (13)
After, enter the second mixing pump (14);Meanwhile, the culture fluid in culture fluid case (3) passes through the second culture fluid
Also into the second mixing pump (14) after pump (12);In the second mixing pump (14), distilled water and culture fluid
Mix by a certain percentage, subsequently into the second microbiological fuel cell (15);Second microbiological fuel cell (15)
The signal of telecommunication of output is amplified into signal processing and display circuit through the second pre-amplification circuit (16)
(10);
The electricity that the first microbiological fuel cell (8) exports analyzed by S12: signal processing and display circuit (10)
RST:
If Ua、IaIt is respectively microbiological fuel cell when the output voltage values in time detection and current value;
Ub、IbIt is respectively output voltage values and the current value of microbiological fuel cell previously certain detection;Or,
For previously certain was several times or the arithmetic mean of instantaneous value of output voltage values of all detections and the arithmetic average of current value
Value;
Then employing below equation calculating toxicity rating Tox:
Tox=(Ua-Ub)/Ub× 100% or Tox=(Ia-Ib)/Ib× 100%
Judge the absolute value of calculated Tox value whether more than predetermined threshold value, if it is greater, then draw by
Survey the conclusion that water sample contains noxious substance, send alarm signal;The first switching valve (4) of switching the most immediately,
Make detected water sample not enter back into the first sense channel, and make distilled water enter the first sense channel, by distillation
The effect of water, protects and recovers the first microbiological fuel cell (8);
S2, then, switching the second switching valve (11), make distilled water not enter back into the second sense channel, and make
Detected water sample enters the second sense channel, is examined the bio-toxicity of detected water sample by the second sense channel
Surveying, the second microbiological fuel cell (15) output analyzed by final utilization signal processing and display circuit (10)
Signal of telecommunication situation, and calculate toxicity rating Tox;Judge that whether the absolute value of calculated Tox value is more than pre-
If threshold value, if it is greater, then draw the conclusion that detected water sample contains noxious substance, send alarm signal;With
Time switch the second switching valve (11) immediately, make detected water sample not enter back into the second sense channel, and make distilled water
Enter the second sense channel, by the effect of distilled water, protect and recover the second microbiological fuel cell (15);
S3, for same detected water sample, if the first sense channel in S1 and the detection of second in S2 are logical
Road all sends alarm signal, it is determined that containing poisonous and harmful substance in detected water sample, now send water quality early-warning
Signal, needs take emergency monitoring and process Disposal Measures;If the first sense channel is reported to the police, is switched to the
Do not report to the police after two sense channels, then need water sample and instrument are done detection further, the most not can determine that tested
Whether water sample contains poisonous and harmful substance.
Preferably, detected water sample and culture fluid mixed proportion and quilt in S2 in the first mixing pump (7) in S1
Survey water sample identical with culture fluid mixed proportion in the second mixing pump (14).
Preferably, in S12, described predetermined threshold value is 50%.
Preferably, in S11, detected water sample enters the first Microbial fuel with culture fluid after mixing by a certain percentage
Battery (8), motor process in the first microbiological fuel cell (8) particularly as follows:
Detected water sample obtains mixed liquor after mixing by a certain percentage with culture fluid;
Mixed liquor uses up flow type water intake mode, it may be assumed that entered microbiological fuel cell originally by water inlet (52)
Body (51), after penetrating anode (54), is flowed out by outlet (53).
What the present invention provided uses microbiological fuel cell to carry out the Apparatus and method for of water quality biological Toxicity Monitoring,
Have the advantage that
(1) this monitoring device is applicable to drinking water source area monitoring, municipal water supply monitoring, lake, river Natural Water
The fields such as body monitoring, sewage treatment plant inflow monitoring, have advantage applied widely;
(2) achieve can the water quality biological Toxicity Monitoring based on microbiological fuel cell of on-line monitoring continuously,
And instrument has higher sensitivity, stable and reliable in work, it is to avoid false alarm.
(3) there is the convenient advantage with life-span length of working service.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in detail:
Microbiological fuel cell is used to carry out water quality biological Toxicity Monitoring as it is shown in figure 1, the present invention provides a kind of
Equipment, can be applicable to the occasions such as monitoring water environment, drinking water monitoring, sewage treatment plant inflow monitoring.
Including: culture fluid case 3, distilled water tank 2, water sample filter the 1, first sense channel, the second sense channel
And signal processing and display circuit 10;
Wherein, the first sense channel include first switching valve the 4, first water sample pump 6, first cultivate liquid pump 5,
First mixing pump the 7, first microbiological fuel cell 8 and the first pre-amplification circuit 9;Water sample filter 1
First output interface of the first output interface and distilled water tank 2 is connected respectively to the input of the first switching valve 4 and connects
Mouthful, the output interface of the first switching valve 4 is connected to the input interface of the first water sample pump 6;Culture fluid case 3
First output interface is connected to the input interface of the first cultivation liquid pump 5;The output interface of the first water sample pump 6 and
First output interface cultivating liquid pump 5 is all connected to the input interface of the first mixing pump 7, the first mixing pump 7
Output interface be connected to the input interface of the first microbiological fuel cell 8, the first microbiological fuel cell 8
Output interface by being connected to signal processing and display circuit 10 after the first pre-amplification circuit 9;
Second sense channel includes that liquid pump 12, second cultivated by second switching valve the 11, second water sample pump 13, second
Mixing pump the 14, second microbiological fuel cell 15 and the second pre-amplification circuit 16;Water sample filter 1
Second output interface of the second output interface and distilled water tank 2 is connected respectively to the input of the second switching valve 11 and connects
Mouthful, the output interface of the second switching valve 11 is connected to the input interface of the second water sample pump 13;Culture fluid case 3
The second output interface be connected to the input interface of the second cultivation liquid pump 12;The output of the second water sample pump 13 connects
Mouth and the second output interface cultivating liquid pump 12 are all connected to the input interface of the second mixing pump 14, and second mixes
The output interface closing pump 14 is connected to the input interface of the second microbiological fuel cell 15, the second microorganism combustion
The output interface of material battery 15 is connected to signal processing and display circuit by after the second pre-amplification circuit 16
10。
Also include: thermostat 17;First microbiological fuel cell the 8, first pre-amplification circuit 9,
It is internal that two microbiological fuel cells 15 and the second pre-amplification circuit 16 are respectively positioned on thermostat 17.
It addition, the model that the parts of following group of the first sense channel are used is logical with the corresponding second detection
Road is identical: the first switching valve 4 and the second switching valve 11;First water sample pump 6 and the second water sample pump 13;
First cultivates liquid pump 5 and second cultivates liquid pump 12;First mixing pump 7 and the second mixing pump 14;First micro-life
Thing fuel cell 8 and the second microbiological fuel cell 15;First pre-amplification circuit 9 and the second preposition amplification
Circuit 16.
As in figure 2 it is shown, the structure of the microbiological fuel cell provided for the present invention, microbiological fuel cell is adopted
By single cell structure, including: microbiological fuel cell body 51, anode 54, negative electrode 56, water inlet 52,
Outlet 53 and separation membrane 55;Wherein, anode and cathode material all use carbon fiber guiding electric material;
Anode 54 is arranged on the inner chamber of microbiological fuel cell body 51, and this inner chamber is separated to form upper inner chamber
57 and lower inner cavity 58;The bottom of lower inner cavity 58 connects with water inlet 52;The circumference of upper inner chamber 57 uniformly sets
Putting at least one outlet 53, such as, outlet is two or four, relatively uniform distribution.It is preferably four
Individual, four outlets are positioned at four sides above anode, it is ensured that water outlet is uniform, without entering in reactor cavity
Water dead band.The top of upper inner chamber 57 arranges separation membrane 55, fits tightly negative electrode 56 on separation membrane 55,
Further, negative electrode 56 is exposed in air.Water inlet 52 and outlet 53 all with oxygen impermeable pvc pipe or
Pump line is connected.
After water sample to be measured mixes with culture fluid, mixed liquor uses up flow type water intake mode, it may be assumed that by water inlet 52
Enter microbiological fuel cell body 51, after penetrating anode 54, outlet 53 flow out.Use up flow type
Water intake mode, it is ensured that water inlet is full of the inner space of whole reactor.
The operation principle of this microbiological fuel cell is: the microorganism of anode apposition growth is by the Organic substance in water
Degraded, the electronics in metabolic process changes into the signal of telecommunication.After noxious substance enters battery, microorganism electrification
Learning activity to reduce, the output signal of telecommunication reduces.By the detection output signal of telecommunication, if the output signal of telecommunication is just compared
When often the signal of telecommunication decreases more than certain percentage ratio (such as 50%), then it is assumed that containing noxious substance in tested water,
Send alarm signal.As it is shown on figure 3, be the graph of relation of microbiological fuel cell output voltage and time.
When water sample comprises material (such as the high-enriched organics) promoting growth of microorganism, microorganism electrification
Learning activity to increase, the output signal of telecommunication increases.If output the signal of telecommunication compare normal electrical signal add certain hundred
Time more than proportion by subtraction (such as 50%), send alarm signal.
Using said apparatus, the use microbiological fuel cell that the present invention provides carries out water quality biological Toxicity Monitoring
Method, as shown in Figure 4, comprise the following steps:
S1, in the case of daily monitoring, the first sense channel enters detected water sample, is used for monitoring detected water sample
Bio-toxicity;Second sense channel enters the distilled water with detected water sample equivalent, as blank;Tool
Body operational circumstances is as follows:
S11: switching the first switching valve 4, makes the output interface of water sample filter 1 and the first water sample pump 6 connect,
And the output interface of distilled water tank 2 and the first water sample pump 6 do not connect;Then, detected water sample filters through water sample
After device 1 filters, filter out the particulate matter in water sample and impurity, it is to avoid pipeline blockage;Then, water after filtration
After sample is by the first switching valve 4 and the first water sample pump 6, enter the first mixing pump 7;Meanwhile, culture fluid case 3
Culture fluid needed for growth of microorganism in microbiological fuel cell is provided, the culture fluid in culture fluid case 3 is led to
Cross first cultivation liquid pump 5 after also into the first mixing pump 7;In the first mixing pump 7, detected water sample and cultivation
Liquid mixes by a certain percentage, and wherein, mixed proportion can be adjusted according to monitoring water sample, typically can arrange
For 1:1;The most mixed mixed liquor enters the first microbiological fuel cell 8;First microbiological fuel cell
The signal of telecommunication of 8 outputs is amplified into signal processing and display circuit 10 through the first pre-amplification circuit 9;
Meanwhile, for the second sense channel, switching the second switching valve 11, the output of distilled water tank 2 is made
Interface and the second water sample pump 13 connect, and the output interface of water sample filter 1 and the second water sample pump 13 do not connect
Logical;Then, after distilled water is by the second switching valve 11 and the second water sample pump 13, the second mixing pump 14 is entered;
Meanwhile, also into the second mixing pump 14 after the culture fluid in culture fluid case 3 passes through the second cultivation liquid pump 12;?
In second mixing pump 14, distilled water mixes by a certain percentage with culture fluid, and mixed proportion mixes with first passage
Ratio is identical;Subsequently into the second microbiological fuel cell 15;The electricity of the second microbiological fuel cell 15 output
Signal is amplified into signal processing and display circuit 10 through the second pre-amplification circuit 16;
The signal of telecommunication feelings of the first microbiological fuel cell 8 output analyzed by S12: signal processing and display circuit 10
Condition:
If Ua、IaIt is respectively microbiological fuel cell when the output voltage values in time detection and current value;
Ub、IbIt is respectively output voltage values and the current value of microbiological fuel cell previously certain detection;Or,
For previously certain was several times or the arithmetic mean of instantaneous value of output voltage values of all detections and the arithmetic average of current value
Value;
Then employing below equation calculating toxicity rating Tox:
Tox=(Ua-Ub)/Ub× 100% or Tox=(Ia-Ib)/Ib× 100%
Judge the absolute value of calculated Tox value whether more than predetermined threshold value, if it is greater, then draw by
Survey the conclusion that water sample contains noxious substance, send alarm signal;Simultaneously the first switching of switching the most immediately valve 4, make by
Survey water sample and do not enter back into the first sense channel, and make distilled water enter the first sense channel, by distilled water
Effect, protects and recovers the first microbiological fuel cell 8;
Concrete, the value of Tox represents the microbiological fuel cell output voltage (or electric current) when secondary detection obtains
Being worth the intensity of variation of relative preceding value, the value of Tox is just, represents that microbiological fuel cell output valve increases, water
Sample there may be the material (such as Organic substance etc.) promoting microorganism electricity generation activity;The value of Tox is negative, represents
Microbiological fuel cell output valve reduce, water sample there may be suppression microorganism electricity generation activity material (as
Heavy metal or organic poison etc.);Tox exceedes certain threshold value (preferably, | Tox | >=50%), then send report
Alert signal.
S2, then, switching the second switching valve 11, make distilled water not enter back into the second sense channel, and make by
Survey water sample and enter the second sense channel, by the second sense channel, the bio-toxicity of detected water sample is detected,
The signal of telecommunication feelings of the second microbiological fuel cell 15 output analyzed by final utilization signal processing and display circuit 10
Condition, and calculate toxicity rating Tox;Judge whether the absolute value of calculated Tox value is more than predetermined threshold value, as
Fruit is more than, then draw the conclusion that detected water sample contains noxious substance, send alarm signal;Switch immediately simultaneously
Second switching valve 11, makes detected water sample not enter back into the second sense channel, and makes distilled water enter the second detection
Passage, by the effect of distilled water, protects and recovers the second microbiological fuel cell 15;
S3, for same detected water sample, if the first sense channel in S1 and the detection of second in S2 are logical
Road all sends alarm signal, the most substantially determines in detected water sample containing poisonous and harmful substance, now sends water quality
Early warning signal, needs take emergency monitoring and process Disposal Measures;If the first sense channel is reported to the police, switching
It is not report to the police after the second sense channel, then can be wrong report, need water sample and instrument are done detection further,
Temporarily not can determine that in detected water sample whether contain poisonous and harmful substance.Used by this two parallel channels one
The mechanism of one confirmation standby, dual, avoids false alarm to greatest extent, it is ensured that the reliability of instrument work,
Protect microbiological fuel cell simultaneously.
The water quality biological Toxicity Monitoring equipment that the present invention provides enters time detected water sample is carried out Toxicity Monitoring, instrument
It is divided into sample introduction and detection process.During sample introduction, detected water sample mix with culture fluid laggard enter microbiological fuel cell,
Nutrient substance in culture fluid maintains the growth of microorganism, and battery can be with continuous firing, it is ensured that instrument continuous
Monitoring.Culture fluid uses deionized water configuration, adds anhydrous sodium acetate and ammonium chloride, and concentration is: anhydrous second
Acid sodium: 1.64g/L, ammonium chloride: 1.5g/L.Feature and advantage on this instrument design be:
(1) each time sample introduction time, front sample needs to be completely exhausted out from battery, it is to avoid when in secondary sample
Poisonous and harmful substance by last diluted sample, thus ensure that monitoring device has preferable sensitivity.
(2), after sample introduction completes, detect again after liquid stops flowing, it is to avoid sample introduction process is to detecting
The interference of journey.
(3) use poison exponent as monitoring index.
(4) it is the reliability guaranteeing monitoring result, employs two or more microbiological fuel cell,
Only when all batteries participating in detection are all reported to the police, instrument just sends water quality early-warning signal.If only one
Individual battery alarm, the probability of battery failures is higher in this case, and now instrument sends single battery warning
Signal, it is simple to malfunction elimination.
(5) microbiological fuel cell and output signal pre-amplification circuit thereof are placed in thermostat, and temperature is permanent
Due to some value of 20-30 DEG C, can be adjusted according to the characteristic of microbiological fuel cell, to guarantee micro-life
Thing has a stable growing environment, farthest ensures equipment precision.
What the present invention provided uses microbiological fuel cell to carry out the Apparatus and method for of water quality biological Toxicity Monitoring,
Have the advantage that
(1) this monitoring device is applicable to drinking water source area monitoring, municipal water supply monitoring, lake, river Natural Water
The fields such as body monitoring, sewage treatment plant inflow monitoring, have advantage applied widely;
(2) achieve can the water quality biological Toxicity Monitoring based on microbiological fuel cell of on-line monitoring continuously,
And instrument has higher sensitivity and work stability and reliability, it is to avoid false alarm.
(3) there is the convenient advantage with life-span length of working service.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
For technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications,
These improvements and modifications also should regard protection scope of the present invention.