CN106338573B - A method of measuring organic acid content in agricultural digester gas engineering anaerobic fermentation system - Google Patents
A method of measuring organic acid content in agricultural digester gas engineering anaerobic fermentation system Download PDFInfo
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- CN106338573B CN106338573B CN201610719584.7A CN201610719584A CN106338573B CN 106338573 B CN106338573 B CN 106338573B CN 201610719584 A CN201610719584 A CN 201610719584A CN 106338573 B CN106338573 B CN 106338573B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
Abstract
The present invention relates to a kind of methods of organic acid content in measurement agricultural digester gas engineering anaerobic fermentation system, including:(1) take anaerobic digestion solution as sample to be tested from biogas engineering anaerobic fermentation system;(2) using dilute acid soln as titrant, the sample to be tested is titrated to pH 5.0, the volume V of record consumption titrant5;(3) titrant is used, continues to titrate the sample to be tested to pH 4.4, the volume V of record consumption titrant4.4;(4) record obtains the sample to be tested same day biogas engineering anaerobic fermentation system creation data;(5) concentration of organic acid in the sample to be tested is calculated according to the titration volumes and creation data.Method provided by the invention is not necessarily to the pretreatments such as centrifuge sample to be tested or filter, it is easy to operate, it is of low cost, as a result accurate, it can be used for the on-site supervision of agricultural digester gas engineering stability early warning, ensure the efficient stable operation of biogas engineering, and then improves the production efficiency of the processing and clean energy resource of agricultural organic waste.
Description
Technical field
The present invention relates to methane engineering technology fields, and in particular in a kind of measurement agricultural digester gas engineering anaerobic fermentation system
The method of organic acid content.
Background technology
It is a kind of important technical that Castoff material energizing utilizes by the biogas engineering of core of anaerobic digestion, is locating
Clean energy resource is generated while managing organic waste, is of great significance to alleviating energy crisis and curbing environmental pollution.Therefore,
Biogas engineering has at home and abroad obtained extensive research application and has flourished.《Chinese agriculture statistics》(2012) it shows, cuts
To 2012, China was built at large, medium and small biogas engineering 9.19 ten thousand, wherein the large-sized biogas engineering of processing agricultural wastes
At 5246, at medium-sized biogas engineering 9767, at small-sized methane engineering 76588;1433.4 ten thousand m of total pool volume3, produce biogas total amount
19.8 hundred million m3.But anaerobic digestion process is substantially being participated in by multiple-microorganism for complexity, the biochemistry orderly carried out stage by stage
Metabolic process, operation stability is affected by various factors, therefore, it is necessary to the key by measuring anaerobic fermentation process
Parameter to be likely to occur stress or instability status carry out early warning, it is high to take appropriate effective measures to ensure that system is stablized in time
Effect operation.
Biogas engineering is generally stablized using the conventional indexs characterization anaerobic digestion process such as monitoring pH value, methane production at present
Property, although these indexs are easy to monitor, due to the cushioning effect of anaerobic System, above-mentioned conventional index is monitored with larger
Hysteresis quality, i.e., for system after unstability, These parameters just will appear large change.Organic acid is important in anaerobic digestion process
Process product, the degradation process that can be appreciated that organic substance is monitored to it, reflects the active degree or biogas engineering of methane backeria
Operating condition.It includes the way of distillation, colorimetric method, chromatography, spectroscopic methodology, titration etc. to measure the method for organic acid at present.At this
In a little test methods, the way of distillation detects limit for height with colorimetric method, and precision is low and complicated for operation, is easily disturbed;Chromatography accuracy is high,
Detection limit is low, can survey separate acid, but disposable input is big, sample pre-treatments are complicated, and professional is needed to operate, in practical work
Universal use is difficult in Cheng Yingyong.There are equipment complexity, the stabilizations of calibration difficulties, in reality as emerging technological means for spectroscopic methodology
It is to be improved that stability is measured in the application process of border.And titration, because its is easy to operate, required experimental facilities is simple, to operator
Member's professional standards require it is low, monitored in biogas engineering field application have it is at low cost, it is easy quickly, accuracy is relatively good
Feature, therefore, titration have been widely recognized and have applied as the effective means of the daily monitoring of biogas engineering.
Titration measuring organic acid is to be based on buffer system balance theory, mainly there is two point Titrations, 4 points of titration at present
Method, five point Titrations and eight point Titrations.It operationally put less since 2 points, four-point method are related to titration, be not required to separately add highly basic,
It is more succinct, quick;In accuracy, since 5 points, 8 methods consider influencing each other for a variety of buffer systems in solution, tie
Fruit is more accurate.In addition, when these methods are used for the measurement of organic acid in biogas engineering anaerobic fermentation system, it usually needs to sample
Product such as are centrifuged, are filtered at the pretreatments, and otherwise the total solid in sample (TS) will increase the consumption of titrant, are caused without centrifugation
Or the titration test result of the sample of filtration treatment is usually higher.Especially for using agricultural wastes as the biogas work of raw material
Journey mostly uses to meet the demand for handling highly filled organic waste and continuously stirs that be thoroughly mixed formula anaerobic digestion anti-
Device (CSTR) and up-flow anaerobic solids reactor (USR) are answered, its main feature is that keeping higher TS in anaerobic fermentation system, generally
It is 6~10%.And to the equipment that sample to be tested carries out centrifugation or filtration treatment needs profession, this undoubtedly increases biogas engineering
The complexity of equipment investment and test method tends not to receive for user.
So far, effective titration method there is no to measure the organic acid content of the fermentation process of agricultural wastes biogas engineering,
Therefore, it is necessary to the basic principle using conventional titration method and its easy characteristic, by the total solid for studying agricultural digester gas engineering
(TS) it to the affecting laws of titration test result, develops and simplifies or omit the pretreated novel titration method measurement of sample to be tested
Organic acid realizes monitoring and early warning to agricultural digester gas engineering.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of characterization agricultural digester gas engineering stability early warning is provided
Organic acid assay method.The method is suitable for handling the biogas engineering anaerobic fermentation system organic acid concentration of agricultural wastes
Daily monitoring, continuous mode is easy to operate without the pretreatments such as being centrifuged or being filtered to sample;This method proposes organic
Sour calculation formula only relates to sample to be tested volume, titrant concentration, twice titrant consumption volume, biogas engineering input and output material and production
Destiny evidence, calculating process is simple, and measurement result is coincide with gas chromatography measurement result, and accuracy is high, can be used for characterizing natural pond
The efficient stable operation of biogas engineering is realized in the stability early warning of gas engineering.
Method provided by the invention includes step in detail below:
(1) it is V that volume is taken from agricultural digester gas engineering anaerobic fermentation systemsampleAnaerobic digestion solution as sample to be tested;
(2) it uses the dilute acid soln that hydrogen ion concentration is c as titrant, titrates the sample to be tested to pH 5.0, record
The volume V of titrant is consumed at this time5;
(3) titrant is used, continues to titrate the sample to be tested to pH 4.4, record consumes the body of titrant at this time
Product V4.4;
(4) record obtains the agricultural digester gas engineering anaerobic fermentation system creation data on the sample to be tested same day;The life
Producing data includes:The same day feeds total solid concentration TSin, same day inlet amount Min, same day methane phase volumeWhen daily output titanium dioxide
Carbon volumeAnd same day load Mout;
(5) volume of the titrant and creation data are substituted into following formula, calculating has in the anaerobic digestion solution
The concentration VFAs of machine acid, the formula are specially:
In the formula, concrete meaning that each parameter represents as:
VFAs:The concentration of organic acid, unit mg/L, with acetic acid in the agricultural digester gas engineering anaerobic fermentation system
(HAc) it counts;
[H in the titrant+] equivalent concentration, unit mol/L;
Vsample:The volume of the sample to be tested, unit mL;
V5:Sample to be tested is titrated from the volume for consuming titrant when initial pH to pH 5.0, unit mL;
V4.4:Sample to be tested is titrated from the volume for consuming titrant when initial pH 5.0 to pH 4.4, unit mL;
TSin:The total solids content (%) of the charging of the agricultural digester gas engineering anaerobic fermentation system;
Min:The agricultural digester gas engineering anaerobic fermentation system same day inlet amount, unit are ton (t);
Mout:The agricultural digester gas engineering anaerobic fermentation system same day load, unit are ton (t);
Methane (CH4) molal weight constant, specially 16g/mol;
The agricultural digester gas engineering anaerobic fermentation system same day methane phase (CH4) volume in normal conditions, it is single
Position is m3;
Carbon dioxide (CO2) molal weight constant, specially 44g/mol;
The agricultural digester gas engineering anaerobic fermentation system is as daily output carbon dioxide (CO2) body in normal conditions
Product, unit m3。
Method provided by the invention is directed to agricultural digester gas engineering anaerobic fermentation system.In the system, fermentation raw material is livestock and poultry
The mixture of excrement, agricultural crop straw or feces of livestock and poultry and agricultural crop straw.The fermentation system is anti-using CSTR types or USR types
Device is answered to carry out fermentation process.The pH of anaerobic digestion solution of the present invention>5.0.
The present invention selects the two specific pH value of pH 5.0 and pH 4.4 as titration point by many experiments, and
Introduced in calculation formula includes that charging total solid concentration, inlet amount, methane phase volume, production carbon dioxide volume and load exist
True creation data is corrected calculating process in interior agricultural digester gas engineering anaerobic fermentation system;So that it is guaranteed that without
To sample to be tested carry out it is any it is pretreated in the case of, it is easy, quickly and accurately obtain testing result.
The agricultural digester gas engineering anaerobic fermentation system input and output material and aerogenesis data, including charging total solid concentration, charging
Amount, methane phase volume, production carbon dioxide volume and load, are the daily monitoring data of agricultural digester gas engineering site, are used
This field conventional method is detected, and the present invention does not do particular determination.
In order to obtain representative sample to be tested, realizes and accurately detect, in the step (1), preferably detest described
Oxygen digestive juice is sufficiently stirred, and sample to be tested is taken out from the central part of stirring.In method provided by the invention, sour drop is carried out
Without being pre-processed to sample before location survey examination.The sample to be tested is titrated immediately after taking out.It is accurate in order to ensure detecting
Operability, V of the present invention are improved while propertysamplePreferably 5~50ml.
The titrant that the present invention uses is preferably dilute hydrochloric acid or dilution heat of sulfuric acid.In order to be realized in rational detection time
Accurate detection, a concentration of 0.1~2mol/L of the preferably described dilute hydrochloric acid of the present invention;It is preferred that a concentration of the 0.05 of the dilute sulfuric acid~
1mol/L.In calculating process, if the titrant is c1Dilute hydrochloric acid (HCl) solution of mol/L, thenIf described
Titrant is c2Dilute sulfuric acid (the H of mol/L2SO4) solution, then
Organic acid content method has easy to operate and can be in reality in titration determination agricultural digester gas engineering of the present invention
The characteristics of border is applied.For two point Titrations need in operation to sample carry out centrifugation or filtration treatment, cause its
The problem of practical application being difficult on the monitoring and warning of agricultural digester gas engineering.The present invention is proposed according to two point Titration basic principles
A kind of titration computation model without sample pretreatment, realizes the easy, fast of the organic acid concentration of agricultural digester gas engineering
The monitoring of speed.Provide technical conditions in the daily monitoring of agricultural digester gas engineering for titration field application, at the same for realize into
The on-line monitoring of organic acid concentration lays the foundation in the agricultural digester gas engineering fermentation system of one step.
Organic acid calculation formula of the present invention only relates to sample to be tested volume, titrant concentration, twice titrant consumption
Volume, biogas engineering input and output material and aerogenesis data, calculating process is easy, and user carries out complexity without tools such as computers
Calculating can obtain final result, grasp and receive convenient for ordinary user.
The present invention is according to two point Titration basic principles, selected titration point only pH 5.0 and pH 4.4 two, equipment used
The only routine experiments equipment such as acid buret, magnetic stirrer, electromagnetic agitation rotor, beaker, it is easy to operate, it is at low cost
It is honest and clean, it grasps and receives convenient for ordinary user.In addition, the present invention is to agricultural digester gas engineering anaerobic fermentation process key parameter organic acid
Measurement result it is accurate, long-term test shows to utilize formula result of calculation of the present invention and gas chromatography (Gas
Chromatography, GC) measurement result coincide, realize agricultural digester gas engineering anaerobic fermentation process organic acid concentration it is accurate
Monitoring, measurement result can in time, accurately reflect the operating condition of biogas engineering, can be likely to occur stress or unstability shape
State carries out early warning.
It is provided by the invention can Vfa Concentration method in the Accurate Determining anaerobic reactor of field application, can be with
Easier, quick, the accurate buffer capacity for judging anaerobic fermentation system, to timely monitoring and warning anaerobic fermentation process
Stability effectively solves the problems, such as that biogas engineering STABILITY MONITORING lags, reduces the operation cost of biogas engineering indirectly, and be
The stable operation of biogas engineering provides technical support with monitoring and warning, to further increase treatment effect and the cleaning of waste
The production efficiency of the energy has good environmental benefit and ecological benefits.
The present invention is at present can there is no the accurate volatile fats of easy to operate, result in practical biogas engineering
Sour monitoring method, innovation has developed one kind can Vfa Concentration side in field application and Accurate Determining anaerobic reactor
Method.It applies it in practical biogas engineering, the accurate measurements of Vfa Concentration in anaerobic reactor may be implemented, from
And the acidification situation of the anaerobic reactor to being likely to occur carries out early warning, takes effective measures in time avoid anaerobic reactor accordingly
Acidification ensures efficient, the stable operation of anaerobic reactor, reduces in biogas engineering because load is excessively high or other reasons cause to detest
The risk hidden danger of oxygen reactor acidification, and reduce the economic loss thereby resulted in.Therefore the invention have wide promotion prospect and
Competitive advantage.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment carries out organic acid concentration in the agricultural digester gas engineering anaerobic fermentation system of CSTR process chicken manures
Detection;Specifically comprise the following steps:
(1) anaerobic digestion solution generated to agricultural digester gas engineering anaerobic fermentation system is stirred, from the centre bit of stirring
It sets and takes volume VsampleFor the anaerobic digestion solution of 20ml subsequent step is directly used in without being pre-processed as sample to be tested
Titration detection;
(2) dilution heat of sulfuric acid of a concentration of 0.05mol/L is used as titrant, titrates the sample to be tested to pH 5.0,
Record consumes the volume V of titrant at this time5=140.9ml;
(3) titrant is used, continues to titrate the sample to be tested to pH 4.4, record consumes the body of titrant at this time
Product V4.4=159.8ml;
(4) record obtains the agricultural digester gas engineering anaerobic fermentation system creation data on the sample to be tested same day;The life
Producing data includes:The same day feeds total solid concentration TSin=8%, same day inlet amount Min=12t, same day methane phase volumeWhen daily output carbon dioxide volumeAnd same day load Mout=12t;
(5) volume of the titrant and creation data are substituted into following formula, calculating has in the anaerobic digestion solution
The concentration VFAs of machine acid, the formula are specially:
It is computed, VFAs=10713.41mg/L in the sample to be tested (with Acetometer).
The acetic acid content in the sample to be tested is detected using conventional gas chromatography, testing result is
11118.54mg/L.As it can be seen that method accuracy in detection provided by the invention is high, and it is more easy to operate than conventional gas chromatography,
It is at low cost.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (12)
1. a kind of method measuring organic acid content in agricultural digester gas engineering anaerobic fermentation system, which is characterized in that including following
Step:
(1) it is V that volume is taken from agricultural digester gas engineering anaerobic fermentation systemsampleAnaerobic digestion solution as sample to be tested;
(2) it uses the dilute acid soln that hydrogen ion concentration is c as titrant, titrates the sample to be tested to pH 5.0, record is at this time
Consume the volume V of titrant5;
(3) titrant is used, continues to titrate the sample to be tested to pH 4.4, record consumes the volume of titrant at this time
V4.4;
(4) record obtains the creation data of the sample to be tested same day agricultural digester gas engineering anaerobic fermentation system;The production number
According to including:The same day feeds total solid concentration TSin, same day inlet amount Min, same day methane phase volumeWhen daily output carbon dioxide body
ProductAnd same day load Mout;
(5) volume of the titrant and creation data are substituted into following formula, calculates organic acid in the anaerobic digestion solution
Concentration VFAs, the formula is specially:
Wherein,For the molal weight constant 16g/mol of methane,For the molal weight constant 44g/mol of carbon dioxide,For [the H in the titrant+] equivalent concentration, unit mol/L.
2. according to the method described in claim 1, it is characterized in that, in the agricultural digester gas engineering anaerobic fermentation system, ferment
Raw material is the mixture of feces of livestock and poultry, agricultural crop straw or feces of livestock and poultry and agricultural crop straw;The fermentation system uses CSTR
Type or USR type reactors carry out fermentation process.
3. according to the method described in claim 2, it is characterized in that, the pH of the anaerobic digestion solution>5.0.
4. according to the method described in claim 1, it is characterized in that, in step (1), the anaerobic digestion solution is fully stirred
It mixes, sample to be tested is taken out from the central part of stirring.
5. method according to claim 1 or 4, which is characterized in that in step (1), from agricultural digester gas engineering anaerobic fermentation
The anaerobic digestion solution taken out in system is titrated immediately without pretreatment.
6. according to the method described in Claims 1 to 4 any one, which is characterized in that the VsampleFor 5~50ml.
7. according to the method described in claim 5, it is characterized in that, the VsampleFor 5~50ml.
8. according to the method described in claim 1, it is characterized in that, the dilute acid soln is dilute hydrochloric acid.
9. according to the method described in claim 8, it is characterized in that, the concentration c of the dilute hydrochloric acid is 0.1~2mol/L.
10. according to the method described in claim 1, it is characterized in that, the dilute acid soln is dilute sulfuric acid.
11. according to the method described in claim 10, it is characterized in that, the concentration c of the dilute sulfuric acid is 0.05~1mol/L.
12. application of the claim 1~11 any one the method in agricultural digester gas engineering stability early warning.
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CN103235085A (en) * | 2013-04-18 | 2013-08-07 | 中国科学技术大学 | Method for rapidly determining volatile fatty acid concentration in anaerobic reactor |
CN104777267A (en) * | 2015-03-30 | 2015-07-15 | 中国农业大学 | Automatic titration device for anaerobic fermentation buffer ability |
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CN103235085A (en) * | 2013-04-18 | 2013-08-07 | 中国科学技术大学 | Method for rapidly determining volatile fatty acid concentration in anaerobic reactor |
CN104777267A (en) * | 2015-03-30 | 2015-07-15 | 中国农业大学 | Automatic titration device for anaerobic fermentation buffer ability |
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