CN103675214B - Device and method for measuring biochemical methane potential (BMP) - Google Patents

Device and method for measuring biochemical methane potential (BMP) Download PDF

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CN103675214B
CN103675214B CN201310719198.4A CN201310719198A CN103675214B CN 103675214 B CN103675214 B CN 103675214B CN 201310719198 A CN201310719198 A CN 201310719198A CN 103675214 B CN103675214 B CN 103675214B
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discharge
fermentation
gas
biochemical methane
inoculum
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CN103675214A (en
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刘荣厚
孙辰
曹卫星
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention provides a device and a method which are used for measuring biochemical methane potential (BMP). The device comprises a fermentation reaction device, a gas collection device and an overflow groove. The method comprises the steps including connection of devices, inspection of the air tightness of a system, pretreatment of an inoculum, preparation of a fermentation liquid, establishment of an oxygen-free and carbon dioxide-free environment, gas collection, replacement of the liquid level of a gas collection tube, measurement of ingredient and calculation of the biochemical methane potential. The method has the advantages of accuracy and reliability in test result, easiness in operation, good repeatability and the like, in addition, the device is simple to build, low in cost, simple in structure, long in service life and small in occupied area.

Description

A kind of apparatus and method measuring biochemical methane potentiality
Technical field
What the present invention relates to is the apparatus and method that a kind of biomass anaerobic digests field, and specifically, what relate to is a kind of apparatus and method measuring biochemical methane potentiality (Biochemical Methane Potential, BMP).
Background technology
As one of the biomass energy mode of production of most prospect, biomass anaerobic digestion produces the technique of biological methane with the biochemical reactions of anaerobe for means, macromolecular organism in living beings is degraded to micromolecular organic acid and gas step by step, completes that to produce with biological methane in the process of organic matter digestion degraded be the new forms of energy of target product simultaneously.In this process, the biochemical methane potentiality of certain living beings are directly related with substrate biomass degradation characteristic, are the target components in fermentation dynamics, simultaneously, biochemical methane potentiality may be used for weighing anaerobic digestion process economy, can as the important parameter evaluating anaerobic digestion process quality.
At present about determinator and the method for biochemical methane potentiality, generally comprise fermentation reaction device, gas collector, the part such as the using method of gasmetry and computing method and device is formed.BMP installation for fermenting two type that fermentation reaction device is divided into static BMP installation for fermenting and stirs continuously.Gas collector has types such as using draining water gathering of gas law, gas pressure sensor method, gas flow measurement method, airbag acquisition method.Biological methane output generally uses vapor-phase chromatography auxiliary measuring, or by method direct reading after methane purifying device, no matter use which kind of method to measure, result is finally converted to the biological methane output under the standard state of unit mass volatile constituent generation.The test of the measurement BMP such as, mentioned in U.S. ASTM standard E2170 – 01 and pertinent literature, relate to and use serum bottle to carry out static fermentation test, serum bottle upper space is used temporarily to store institute's aerogenesis body, use the change of gaseous tension in pressure transducer record serum bottle and the gas volume under pressure data being converted to standard state, the mixed gas periodically accumulated in release serum bottle also measures mixed gas content.This method working specification is reproducible, but owing to using the round of given volume simultaneously as the storage place of gas, the carbon dioxide in the mixed gas produced often is caused to be dissolved in fermentation liquor with the form of carbonate and bicarbonate radical under higher than atmospheric state, the test error that the measured value of biological methane is bigger than normal can be introduced first, two change the acid-base equilibrium systems under fermentation liquor state of nature, make fermentation liquor meta-acid, cause test findings cannot react the real biodegradability of living beings and biochemical methane potentiality.Although front a kind of error can be corrected by using the mode of alkali lye residual titration fermentation liquor to recalculate biochemical methane amount after fermentation ends, but this adds workload and the complexity of test undoubtedly, the second experiment abberation also cannot be corrected by other means all the time simultaneously.In addition, these apparatus and method relate to and use pressure transducer to measure the reaction institute aerogenesis scale of construction, need extra power supply input and the manufacture craft more complicated of device, if buy commercially produced product, need larger expense, due to cost that life of product problem also needs repairing and changes in use procedure.
Also there is corresponding deficiency in determinator and the method for some other biochemical methane potentiality.The installation for fermenting of continuous stirring can ensure that material fully mixes, more applicable for the substrate easily playing scum silica frost and foaming, but its advantage only shows limited use field, its shortcoming is that its cost of manufacture is high, need additional electrical energy input to maintain to stir, maintenance cost is high, and the motor of stirring apparatus also has certain serviceable life.About gas collector, draining water gathering of gas law is simple to operation, and the device simple structure life-span is long, and maintenance cost is low.But in a lot of cases before, implementer often considers too simple, equipment Design and making, collection and computing method extensive, use the volume of the water of discharging to represent the volume of institute's aerogenesis body, introduce a lot of error, acquired results cannot represent the actual value of test.Also have and a kind ofly use alkali lye to carry out draining gas collection or by increase extra device, the carbon dioxide in mixed gas removed to the method for the output then measuring biological methane, but this method is except having the ubiquitous problem of draining water gathering of gas law, also exist and really cannot ensure the problem removing all carbon dioxide, bring error to test findings, make result bigger than normal.Gas flow measurement method operates simple saving of labor, but needs certain cost of manufacture, relates generally to the principle of draining counting, and calculating and antidote exist same problem with traditional draining water gathering of gas law.Simultaneously when last stage reaction gas flow is lower, its precision often cannot be satisfied the demand.And use airbag to collect the gas sampling bag (as Tedlar gas production bag) extremely low to gas molecule Penetration ration of rule needs selection high price to ensure the reliability of impermeability and test findings.The mensuration of simultaneously carrying out volume to the gas collected again relates to and calculates reliably and the problem of antidote.
Therefore, those skilled in the art are devoted to develop a kind of apparatus and method measuring biochemical methane potentiality, make device be easy to build, condition is easy to control, the measuring error that in measuring process, carbon dioxide is introduced can be eliminated, solve the problem of fermentation liquor meta-acid, reduce the difficulty of correcting, improve the accuracy measured.
Summary of the invention
Because prior art is in the measurement of biochemical methane potentiality, the deficiency that device is complicated, easily produce error, result correcting process complexity, technical matters to be solved by this invention is to provide a kind of apparatus and method measuring biochemical methane potentiality, use the installation for fermenting and gas extractor establishment test device systematic that are easy to build, be easy to control, adopt the strong pivotal trial step Control experiment condition of controllability and science to calculate the method for sending out reliably and realize for the biodegradability of a certain specific biomass and the Accurate Determining of biochemical methane potentiality.
The present invention solves by the following technical programs and solves the problems of the technologies described above:
A kind of device measuring biochemical methane potentiality is provided, comprises: fermentation reaction device, gas collecting device, overflow groove.This fermentation reaction device comprises thermostat and tool plug fermentation flask.
This gas collecting device comprises aqua storage tank, discharge support, discharge and vacuum pump.This tool plug fermentation flask is placed in thermostat, and tool plug fermentation flask is connected with the bottom of discharge by the first wireway; Discharge keeps the plumbness with surface level by discharge support, comprise the passage that wireway can be made by access set tracheae, discharge and discharge prop up and are placed in aqua storage tank, discharge top comprises a gas outlet, gas outlet is connected with T-valve, and T-valve is connected with vacuum pump by the second wireway; The upper portion side wall of aqua storage tank is provided with overflow vent, and overflow vent is connected with overflow groove by the first aqueduct, and overflow groove is also connected with aqua storage tank by the second aqueduct, forms the loop of current, the second aqueduct is provided with constant flow pump.NaCl saturated solution in aqua storage tank is overflowed by overflow vent and the first aqueduct, by constant flow pump by the blowback of NaCl saturated solution to aqua storage tank, maintain water level in aqua storage tank and do not reduce because of solution evaporation and other reasons.Tool plug fermentation flask, by using anaerobic environment in the strict airtight bottle of single hole rubber plug at bottleneck, leads to the first wireway to gas collecting device by single hole.
Preferably, the device of these measurement biochemical methane potentiality also comprises tool hole insulation cover, and thermostat is constant temperature water bath apparatus, and tool hole insulation cover matches with constant temperature water bath apparatus, for reducing the exchange of water bath and extraneous temperature and steam.Tool plug fermentation flask is positioned in constant temperature water bath apparatus by the hole on the insulation cover of tool hole.
Further, the lower sides of discharge is provided with hole, and the first wireway is connected with this hole.
Further, first wireway is provided with variable valve, closing this variable valve can path between blocking fermentation reaction unit and gas collecting device, thus carries out the bubble-tight inspection of system, and carries out the foundation without carbon dioxide environment to gas collecting device.This variable valve can be T-valve.
Preferably, T-valve is also connected with sampling thief, can gather gaseous sample by this sampling thief, for the analysis of gas componant.This sampling thief is preferably the syringe of 5-20mL.
Further, the tube wall of discharge is provided with scale, and 0 scale mark of described scale is positioned at the top of discharge, near the sealed end of discharge, can be read the height of liquid level distance 0 scale mark by this scale accurately.Preferably, described scale is precision is 1mm scale, and 0 scale mark is positioned at the top of discharge.
The present invention also provides a kind of method utilizing said apparatus to measure biochemical methane potentiality, comprises following steps:
(1) complete the connection between the fermentation reaction device of said apparatus, gas collecting device and overflow groove and airtight test is carried out to this device; Wherein, connection refers to and utilizes wireway and aqueduct to be coupled together by device, uses single hole rubber plug sealed fermenting bottle;
(2) pre-service is carried out to inoculum, comprises after inoculum is filtered, inoculum is put into constant incubator activate many days for subsequent use; Wherein, filter the inoculum referring to and use the screen cloth in 1-2mm aperture to collect, as fresh activity anaerobic sludge filters, remove the particulate matter affecting homogeneity, and activate 3 days;
(3) fermentation liquor preparation, comprises with volatile solids content for benchmark, uses inoculum and the living beings substrate preparation fermentation liquor of activation, puts into tool plug fermentation flask, and ensure the technological condition for fermentation meeting testing requirements; And preparation is only containing the blank fermentation liquor of inoculum, to carry out blank test; And preparation uses the inoculum of activation and the positive control fermentation liquor of the cellulose of identical volatile solid quality as substrate; 2 parallel experiments are at least done in each process.Meanwhile, add nutriment in fermentation liquor to ensure that the concentration of nutriment in fermentation liquor meets the demand of microorganism, above-mentioned nutriment comprises: NH 4cl, NaCl, MgCl 26H 2o, CaCl 22H 2o, K 2hPO 43H 2o, NaAc, CoCl 26H 2o, (NH 4) 6mo 7o 244H 2o, NiCl 22H 2o, Na 2seO 3, Na 2wO 42H 2o;
(4) anaerobic is without the foundation of carbon dioxide environment, comprises and uses vacuum pump by the NaCl saturated solution pump in described aqua storage tank to the top of described discharge, use air-flow blowback method to make to be formed without carbon dioxide environment in described discharge; Gas flow purging method is used to make to form anaerobic in tool plug fermentation flask without carbon dioxide environment;
(5) gas collecting and discharge liquid level reset, be included in before liquid level in discharge to drop in aqua storage tank below liquid level, periodically use vacuum pump by liquid level resorption in discharge to the top of discharge, the anaerobic then in use air-flow blowback method maintenance discharge is without carbon dioxide environment;
(6) composition measurement, after comprising the measurement data reading discharge, before carrying out the replacement of discharge liquid level, gathers gaseous sample from the top of discharge, to carry out the mensuration of gas componant;
(7) calculating of biochemical methane potentiality, be included in living beings be substrate and with cellulose be substrate test acquired results in deduct the acquired results of blank test;
Preferably, the gas purging method in step (4) refers to and uses N 2purge the headroom of tool plug fermentation flask, discharge air, use rapidly the single hole rubber stopper seal fermentation flask being connected to wireway subsequently; Gas blowback method in step (4) and step (5) refers to and uses N 2by the liquid level blowback in discharge to 0 scale place of discharge sidewall scale.
Preferably, in step (3), the working volume of fermentation liquor is 80% of tool plug fermentation flask cumulative volume, and concentration is 10-70g VS/L.Usually, the mass ratio of inoculum and the volatile solid shared by substrate is 0.5-6.
Further, the calculating of the biochemical methane ability of step (7) uses following formula to carry out:
BMP stp = Σ i = 1 n T stp * ( A * h i * % CH 4 , i * ( p i - p H 2 O , T i - ρ ss , NaCl * g * ( H - h i ) ) + p i V i ) T i * p stp VS substrate .
Wherein, BMP stp: the biochemical methane potentiality under substrate standard state;
Perform step (5) and (6) i: the i-th time;
N: experimental stage performs n step (5) and (6) altogether;
A: the cross-sectional area of described discharge;
H i: the height that during i-th execution step (5), in described discharge, liquid level declines;
T stp: the temperature under standard state;
%CH 4, i: the methane relative content performing gained time step (6) for i-th time;
P i: the atmospheric pressure performed time step (5) for i-th time;
P h2O, Ti: the saturated vapor pressure of NaCl saturated solution during i-th execution step (5);
ρ ss, NaCl: the density of NaCl saturated solution;
G: local acceleration of gravity;
H: the height at the liquid level distance set tracheae top in aqua storage tank;
V i: the gas volume performing sampling time step (6) for i-th time;
T i: the environment temperature performed time step (5) for i-th time;
P stp: the atmospheric pressure under standard state;
VS substrate: the amount of volatile material in living beings substrate in described fermentation liquor.
Device of the present invention is easy to build, design science, and controllability is strong, is strictly controlled, the repeatability of warranty test by environmental factor and inner anaerobic to external world without carbon dioxide environment; Outside system institute aerogenesis body discharge system immediately, ensure the stability of yeasting; Include the variable factors such as external atmosphere pressure, temperature, Saturated water vapor pressure in computing system, ensure the comparability of acquired results; By using blank and positive control, ensure accuracy and the credibility of data; In sum, compared with prior art, the advantages such as the present invention has test result accurately and reliably, easy to operate, reproducible, build simple and easy with timer, cost is low, and structure is simple, and long service life, floor area is little.
Below with reference to accompanying drawing, technical scheme of the present invention is described further, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiments of the invention 1.
Fig. 2 is pig manure biochemical methane Potential curves figure of the present invention.
Embodiment
Embodiment 1
As shown in Figure 1, the device of measurement biochemical methane potentiality of the present invention mainly comprises: fermentation reaction device 1, gas collecting device 2 and overflow groove 3.Fermentation reaction device 1 comprises: constant temperature water bath apparatus 4, tool hole insulation cover 5, tool plug fermentation flask 6 and variable valve 14.Gas collecting device 2 comprises: aqua storage tank 7, discharge support 8, discharge 9, vacuum pump 10, overflow vent 11, constant flow pump 12, T-valve 15 and sampling thief 13.In fermentation reaction device 1, tool plug fermentation flask 6 is connected by the discharge 9 bottom aperture of the first wireway with gas collecting device 2 that variable valve 14 is housed.Gas collecting device is connected with overflow groove 3 with the first aqueduct on overflow vent by overflow vent 11, and overflow groove 3 is also connected with gas collecting device 2 by the second aqueduct that constant flow pump 12 is housed.
In fermentation reaction device 1, constant temperature water bath apparatus 4 is for maintaining fermentation temperature at design temperature.Tool hole insulation cover 5 has cube frame structure, its bottom opening, and top has circular port, and the diameter of this circular port is slightly larger than the diameter of tool plug fermentation flask 6, and with sacrificial vessel plug fermentation flask 6 through circular port, body is arranged in constant temperature water bath apparatus 4.Tool hole insulation cover 5 is inverted in constant temperature water bath apparatus 4, the height of tool hole insulation cover 5 is higher than the liquid level of constant temperature water bath apparatus 4, water bath shampoo near tool plug fermentation flask 6 and outside air environment are isolated, to reduce the exchange of water bath and extraneous temperature and steam.Certainly, in other embodiments, the shape of tool hole insulation cover 5 also can be board-type or other shapes, as long as the water bath shampoo near tool plug fermentation flask 6 and outside air environment can be isolated.
Tool plug fermentation flask 6 is the narrow-mouthed bottle of 150-2000mL, for carrying out the microbial reaction process of biochemical methane potentiality mensuration.Those skilled in the art are known, and this tool plug fermentation flask 6 can be serum bottle or other substitute products similar.Tool plug fermentation flask 6 bottleneck uses the strict sealed fermenting bottle of single hole rubber plug, keeps the anaerobic environment in it.In another embodiment, constant incubator can also be used as thermostat.
Tool plug fermentation flask 6 is connected by the aperture of discharge 9 bottom of the first wireway with gas collecting device 2 that variable valve 14 is housed.The gas produced in tool plug fermentation flask 6 is by the first wireway, and the aperture via discharge 9 bottom enters gas collecting device 2, and the position of this aperture is lower than the balance liquid level of aqua storage tank 7.Discharge 9 is for having the tubular container of certain altitude, and comprise an openend and a sealed end, openend is placed in aqua storage tank 7, sealed end comprises a gas outlet, this gas outlet is connected with T-valve 15, and sealed end is positioned at the top of discharge 9, and openend is positioned at the bottom of discharge 9.Longitudinal wall of discharge 9 contains the scale that precision is 1mm scale, and 0 scale mark is positioned at the top of discharge 9.
Vacuum pump 10 is connected by the T-valve 15 of the second wireway with discharge 9 top, vacuum pump 10 for periodic duty by NaCl solution pump saturated in aqua storage tank 7 to the top of discharge 9.3rd end of T-valve 15 is connected with sampling thief 13, and gaseous sample is gathered by sampling thief 13, can be used for the analysis carrying out gas componant.Discharge 9, by discharge support 8 effect of providing support, keeps and horizontal plane state.Discharge support 8 is vertically placed in aqua storage tank 7, comprises and the first wireway can be made to pass through and the passage of access set tracheae 9.In aqua storage tank 7, saturated NaCl solution is communicated with by the lower openings of discharge 9 with saturated NaCl solution in discharge 9.
Aqua storage tank 7 side has overflow vent 11, is connected with overflow groove 3 by the first aqueduct on overflow vent 11, and overflow groove 3 is also connected with gas collecting device 2 by the second aqueduct that constant flow pump 12 is housed.By the effect of constant flow pump 12 and overflow vent 11, maintain the water level balancing liquid level in aqua storage tank 7 constant.
Embodiment 2
The method realizing measuring biochemical methane potentiality based on said apparatus comprises following steps: the connection of (1) finishing device and device airtight test; (2) inoculum pre-service; (3) fermentation liquor preparation; (4) anaerobic is without the foundation of carbon dioxide environment; (5) gas collecting and discharge liquid level reset; (6) composition measurement; (7) calculating of biochemical methane potentiality.
(1) connection of finishing device and the airtight test of device.
Needed before on-test to use the wireway of certain specification and aqueduct to be coupled together by device each several part, use single hole rubber plug airtight tool plug fermentation flask 6, and air tight test is carried out to device total system.Concrete grammar can adopt following measures: use vacuum pump 10 by saturated NaCl solution pump to 0 scale mark place of collector pipe 9.Closure set tracheae 9 top T-valve 15, opens the first wireway place variable valve 14, leaves standstill device 48h, to observe in collector pipe 9 liquid level with or without lower than 0 scale mark.If lower than 0 scale mark, the place that may leak gas is investigated, till when air tight test, liquid level can maintain 0 scale mark 48h.
(2) inoculum pre-service.
While pick-up unit leakproofness, pre-service is carried out to inoculum.The excess sludge that inoculum produces from sewage treatment plant's anaerobic digestion process, or the natural pond slag that biogas engineering anaerobic digestion process produces gathers.Gathering after inoculum uses the screen cloth in 1-2mm aperture the fresh activity anaerobic sludge collected to be filtered the particulate matter removed and affect homogeneity, the constant incubator then putting into fermentation test temperature required (such as 36 DEG C) activate 3 days for subsequent use.
(3) fermentation liquor preparation.
Meanwhile, the moisture of substrate and inoculum, total solids content and volatile solid content is tested.After device air tight test is carried out pre-service by, inoculum and is obtained the volatile solid content value of substrate and inoculum, with volatile solids content for benchmark, use the inoculum and substrate preparation fermentation liquor that have just activated, put into tool plug fermentation flask 6, make its working volume be 80% of tool plug fermentation flask 6 cumulative volume, fermentation liquor concentration is 10-70gVS/L.Wherein VS represents volatile solid, refers to the part solid that can volatilize under 550 DEG C of high temperature in total solid.Usually, the mass ratio of inoculum and the volatile solid shared by substrate is 0.5-6.Do only containing the blank of inoculum, with the positive control of cellulose as substrate using identical volatile solid quality simultaneously.And with living beings be substrate and with cellulose be substrate test acquired results in deduct the acquired results of blank test.Inoculum being decomposed the biological methane self produced gets rid of outside test value to use the object of blank to be.The repeatability using the object of positive control to be to check this to test by the known organism that can be decomposed completely and reliability, it is generally acknowledged that positive controls completes the biodegradation process accounting for theoretical value more than 70%, and the percentage error between positive controls parallel experiment is less than 5%, this test is efficiency test.3 parallel experiments are at least done in each process.
Meanwhile, in fermentation liquor, add nutriment, ensure the ultimate density of nutriment in fermentation liquor as listed in table 1:
The ultimate density of table 1 nutriment in fermentation liquor
Nutriment Concentration
NH 4Cl 1g/L
NaCl 0.1g/L
MgCl 2·6H2O 0.1g/L
CaCl 2·2H2O 0.05g/L
K 2HPO 4·3H 2O 0.4g/L
NaAc 0.25g/L
CoCl 2·6H2O 0.4mg/L
(NH 4) 6Mo 7O 24·4H 2O 0.02mg/L
NiCl 2·2H 2O 0.4mg/L
Na 2SeO 3 0.02mg/L
Na 2WO 4·2H 2O 0.02mg/L
(4) anaerobic is without the foundation of carbon dioxide environment.
Before on-test, use vacuum pump 10 by the saturated NaCl solution pump in aqua storage tank 7 to discharge 9 top, use T-valve 15 and use N 2gas flow optimized liquid level to 0 scale mark place, the anaerobic in formation discharge is without carbon dioxide environment.And use flow velocity to be greater than the N of 100ml/min 2gas flow purging tool plug fermentation flask 6 headroom, the N of purging 2volume at least 3 times is to the headroom of tool plug fermentation flask 6.Then use rapidly the single hole rubber stopper seal tool plug fermentation flask 6 being connected to the first wireway, the anaerobic in formation tool plug fermentation flask 6 is without carbon dioxide environment.Tool plug fermentation flask 6 is fixed on and sets in the constant temperature water bath apparatus 4 of temperature, and passes the hole of tool hole insulation cover 5, and thus, test formally starts.The state that after on-test, every day, hand tool plug fermentation flask once kept fermentation liquor to mix.
(5) gas collecting and discharge liquid level reset.
After on-test, produce biogas due to the microbial activities in tool plug fermentation flask 6, lead to via the first wireway the collection that discharge 9 carries out gas.Before below each liquid level that liquid level drops in aqua storage tank 7 in discharge 9, read the measurement data shown by the scale of discharge 9, and read atmospheric pressure and temperature at that time by atmospheric pressure meter and thermometer, then periodically use vacuum pump 10, by T-valve 15, liquid level resorption in discharge 9, to top, is then used N 2by discharge 9 top liquid level blowback to 0 scale place, the anaerobic in maintenance discharge 9 is without carbon dioxide state.
(6) composition measurement.
After the measurement data of each reading discharge 9, before the liquid level carrying out discharge 9 resets, carried out the collection of gaseous sample by gas sampler 13 by the 3rd end of the T-valve 15 on discharge 9 top, gas sampler 13 is the syringe of 5-20mL.Accurate acquisition gas 2.0-10.0mL, uses vapor-phase chromatography to measure gas componant, obtains the relative content in mixed gas of methane, and add the amount gathering gas in the result.
(7) calculating of biochemical methane potentiality.
When the biological methane amount that the fermentation test being substrate with certain living beings produces deduct biological methane amount that blank test produces no longer change time, be considered as off-test.Now, the biochemical methane potentiality calculating certain living beings use following computing formula to carry out:
BMP stp = Σ i = 1 n T stp * ( A * h i * % CH 4 , i * ( p i - p H 2 O , T i - ρ ss , NaCl * g * ( H - h i ) ) + p i V i ) T i * p stp VS substrate .
Wherein, BMP stp: the biochemical methane potentiality under substrate standard state;
Perform step (5) and (6) i: the i-th time;
N: experimental stage performs n step (5) and (6) altogether;
A: the cross-sectional area of described discharge;
H i: the height that during i-th execution step (5), in described discharge, liquid level declines;
T stp: the temperature under standard state;
%CH 4, i: the methane relative content performing gained time step (6) for i-th time;
P i: the atmospheric pressure performed time step (5) for i-th time;
P h2O, Ti: the saturated vapor pressure of NaCl saturated solution during i-th execution step (5);
ρ ss, NaCl: the density of NaCl saturated solution;
G: local acceleration of gravity;
H: the height at the liquid level distance set tracheae top in aqua storage tank;
V i: the gas volume performing sampling time step (6) for i-th time;
T i: the environment temperature performed time step (5) for i-th time;
P stp: the atmospheric pressure under standard state;
VS substrate: the amount of volatile material in living beings substrate in described fermentation liquor.
Embodiment 3
Use the fresh pig manure originated within 1 day to be raw material, to take from the anaerobic sludge of Shanghai City Bai Longgang sewage treatment plant mesophilic anaerobic digestion tank for inoculum, utilize device of the present invention to implement method of the present invention.In this test, inoculum initial pH value is 7.35, and inoculum volatile solid content of material is 2.1%, and working volume is 0.4L, and the volatile solid matter mass ratio of inoculum and substrate is 2, and concentration of substrate is 10g VS/L, and inoculum concentration is 20g VS/L.Fermentation temperature 36 ± 1 DEG C, every day hand fermentation flask once.Pig manure and positive control test group in the end discharge in result inoculum itself produce thing methane content.As shown in Figure 2, in this test, the biochemical methane potentiality of pig manure are 251.4mL CH 4/ g VS, the biochemical methane potentiality of positive control are 399.1mL CH 4/ g VS, inoculum biochemical methane potentiality are 77.5mL CH 4/ g VS.Positive controls three parallel experiment medial error number percents are respectively 3.3%, 3.6% and 4.5%, and test effectively.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (10)

1. measure a device for biochemical methane potentiality, comprising: fermentation reaction device, gas collecting device, overflow groove, is characterized in that:
Described fermentation reaction device comprises thermostat and tool plug fermentation flask;
Described gas collecting device comprises aqua storage tank, discharge support, discharge and vacuum pump;
Described tool plug fermentation flask is placed in thermostat, and described tool plug fermentation flask is connected by the bottom of the first wireway with described discharge; Described discharge keeps the plumbness with surface level by described discharge support, described discharge and described discharge prop up and are placed in described aqua storage tank, described discharge comprises sealed end and openend, lay respectively at the both sides of described discharge, described openend is placed in described aqua storage tank, described sealed end comprises a gas outlet, and described gas outlet is connected with T-valve, and described T-valve is connected with described vacuum pump by the second wireway; The upper portion side wall of described aqua storage tank is provided with overflow vent, and described overflow vent is connected with described overflow groove by the first aqueduct, and described overflow groove is also connected with described aqua storage tank by the second aqueduct, and described second aqueduct is provided with constant flow pump.
2. the device of measurement biochemical methane potentiality according to claim 1, it is characterized in that, also comprise tool hole insulation cover, described thermostat is constant temperature water bath apparatus, described tool hole insulation cover matches with described constant temperature water bath apparatus, for reducing the exchange of water bath and extraneous temperature and steam, described tool plug fermentation flask is positioned in described constant temperature water bath apparatus by the hole on the insulation cover of described tool hole.
3. the device of measurement biochemical methane potentiality according to claim 2, it is characterized in that, the lower sides of described discharge is provided with hole, and described first wireway is connected with described hole.
4. the device of measurement biochemical methane potentiality according to claim 3, is characterized in that, described first wireway is provided with variable valve.
5. the device of measurement biochemical methane potentiality according to claim 1, it is characterized in that, described T-valve is also connected with sampling thief.
6. the device of measurement biochemical methane potentiality according to claim 1, it is characterized in that, the tube wall of described discharge is provided with scale, and 0 scale mark of described scale is positioned at the top of discharge, near described sealed end.
7. utilize a method for measurement device biochemical methane potentiality as claimed in claim 1, it is characterized in that, comprise following steps:
(1) complete the connection between the described fermentation reaction device of described device, described gas collecting device and described overflow groove, and airtight test is carried out to described device;
(2) pre-service is carried out to inoculum, comprises after described inoculum is filtered, described inoculum is put into constant incubator activate many days for subsequent use;
(3) fermentation liquor preparation, comprises with volatile solids content for benchmark, uses the described inoculum of activation and living beings substrate to prepare described fermentation liquor, puts into described tool plug fermentation flask; And preparation is only containing the blank fermentation liquor of described inoculum, to carry out blank test; And preparation uses the described inoculum of activation and the positive control fermentation liquor of the cellulose of identical volatile solid quality as substrate, to carry out positive control test;
(4) anaerobic is without the foundation of carbon dioxide environment, comprises and uses vacuum pump by the NaCl saturated solution pump in described aqua storage tank to the top of described discharge, use air-flow blowback method to make to form anaerobic in described discharge without carbon dioxide environment; Gas flow purging method is used to make to form anaerobic in described tool plug fermentation flask without carbon dioxide environment;
(5) gas collecting and discharge liquid level reset, before being included in below liquid level that liquid level in described discharge drops in described aqua storage tank, periodically use described vacuum pump by liquid level resorption in described discharge to the top of described discharge, then use described air-flow blowback method to maintain anaerobic in described discharge without carbon dioxide environment;
(6) composition measurement, comprises and gathers gaseous sample from the top of described discharge, to carry out the mensuration of gas componant;
(7) calculating of biochemical methane potentiality, to be included in order to living beings be the fermentation liquor of substrate preparation and take cellulose as the acquired results deducting blank test in the test acquired results that carries out of the fermentation liquor of substrate preparation.
8. the method for measurement biochemical methane potentiality according to claim 7, is characterized in that, the gas purging method in step (4) refers to and uses N 2purge the headroom of described tool plug fermentation flask, discharge air; Described gas blowback method in step (4) and step (5) refers to and uses N 2by the liquid level blowback in described discharge to 0 scale place of described discharge.
9. the method for measurement biochemical methane potentiality according to claim 7, it is characterized in that, in described step (3), the working volume of described fermentation liquor is 80% of the cumulative volume of described tool plug fermentation flask, concentration is 10-70g VS/L, and the mass ratio of described inoculum and the volatile solid shared by described living beings substrate is 0.5-6.
10. the method for measurement biochemical methane potentiality according to claim 7, is characterized in that, described step (7) uses following formula to carry out:
Wherein, BMP stp: the biochemical methane potentiality under substrate standard state;
Perform step (5) and (6) i: the i-th time;
N: experimental stage performs n step (5) and (6) altogether;
A: the cross-sectional area of described discharge;
H i: the height that during i-th execution step (5), in described discharge, liquid level declines;
T stp: the temperature under standard state;
%CH 4, i: the methane relative content performing gained time step (6) for i-th time;
P i: the atmospheric pressure performed time step (5) for i-th time;
P h2O, Ti: the saturated vapor pressure of NaCl saturated solution during i-th execution step (5);
ρ ss, NaCl: the density of NaCl saturated solution;
G: local acceleration of gravity;
H: the height at the liquid level distance set tracheae top in aqua storage tank;
V i: the gas volume performing sampling time step (6) for i-th time;
T i: the environment temperature performed time step (5) for i-th time;
P stp: the atmospheric pressure under standard state;
VS substrate: the amount of volatile material in living beings substrate in described fermentation liquor.
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