DE202008003790U1 - Device for fast on-line measurement in biogas - Google Patents
Device for fast on-line measurement in biogas Download PDFInfo
- Publication number
- DE202008003790U1 DE202008003790U1 DE200820003790 DE202008003790U DE202008003790U1 DE 202008003790 U1 DE202008003790 U1 DE 202008003790U1 DE 200820003790 DE200820003790 DE 200820003790 DE 202008003790 U DE202008003790 U DE 202008003790U DE 202008003790 U1 DE202008003790 U1 DE 202008003790U1
- Authority
- DE
- Germany
- Prior art keywords
- biogas
- automatic
- measurement
- measuring
- chemometric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005259 measurement Methods 0.000 title claims abstract description 13
- 238000001228 spectrum Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000012491 analyte Substances 0.000 claims abstract 2
- 239000012065 filter cake Substances 0.000 claims abstract 2
- 238000004886 process control Methods 0.000 claims abstract 2
- 238000001179 sorption measurement Methods 0.000 claims abstract 2
- 238000004497 NIR spectroscopy Methods 0.000 claims 1
- 238000001069 Raman spectroscopy Methods 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 238000011156 evaluation Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims 1
- 238000004846 x-ray emission Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012569 chemometric method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000513 principal component analysis Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2247—Sampling from a flowing stream of gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/638—Specific applications or type of materials gas
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Vorrichtung
zur automatischen und vorbehandlungsfreien und onlinefähigen Messung
von Biogasparametern mit
• Einem
Automaten zur automatischen Probenbereitstellung, evtl. Anreicherung
und Messung von Proben aus dem Labor oder aus Fließsystemen
• Einem Adsorptionsapparat
zur automatischen Erhöhung der
Analytkonzentration
• Einer
Vorrichtung zur automatischen Überführung des
Biogases in eine Messapparatur bzw. zur Zuführung einer Sende- und Empfangsoptik
zum Filterkuchen
• Einem
Spektrometer zur automatischen Vermessung des Extrakts
• Einem chemometrischen
Kalibrationsmodell zur Auswertung des aktuellen Spektrums hinsichtlich
der chemischen, physikochemischeb und physikalischen Biogaseigenschaften
• Einem elektronischen
System zur Umsetzung der chemometrisch-spektroskopischen Resultate in ein übertragbares Signal
beispielsweise zur ProzesssteuerungDevice for the automatic and pretreatment-free and online-capable measurement of biogas parameters with
• A vending machine for automatic sample preparation, possibly enrichment and measurement of samples from the laboratory or from flow systems
An adsorption apparatus for automatically increasing analyte concentration
• A device for automatically transferring the biogas into a measuring apparatus or for feeding a transmitting and receiving optics to the filter cake
• A spectrometer for automatic measurement of the extract
• A chemometric calibration model to evaluate the current spectrum for chemical, physicochemical and physical biogas properties
• An electronic system for converting the chemometric-spectroscopic results into a transferable signal for process control, for example
Description
Hintergrundbackground
Biogasanlagen sind in der Lage, den in organischem Material enthaltenen Kohlenstoff bzw. den darin chemisch gespeicherten Energieinhalt zu einem sehr hohen Prozentsatz in effizient nutzbaren Brennstoff umzuwandeln.biogas plants are capable of containing the carbon contained in organic material or the energy content chemically stored therein to a very convert high percentage into efficiently usable fuel.
Es entsteht dabei ein Gasgemisch, welches hauptsächlich aus Methan, Kohlendioxid und Ammoniak sowie als Nebenbestandteilen aus Schwefelwasserstoff, Alkoholen, Aldehyden, Ketonen, Säuren und höheren Kohlenwasserstoffen zusammengesetzt ist.It arises while a gas mixture consisting mainly of methane, carbon dioxide and ammonia and as minor constituents of hydrogen sulphide, Alcohols, aldehydes, ketones, acids and higher Hydrocarbons is composed.
Diese Zusammensetzung ist vom Anlagenzustand und von der Art und dem Zustand der Einsatzmaterialien abhängig. Insofern ist die Biogaszusammensetzung immer relativ starken Schwankungen unterworfen, dies gilt auch für Summenparameter wie z. B. den Wobbe-Index.These Composition is of plant condition and style and condition dependent on the feed materials. In this respect, the biogas composition is always relatively strong fluctuations subject, this also applies to Sum parameters such. For example, the Wobbe index.
Um die Qualität des Produkts und die optimale Betriebsweise der Biogasanlage nachweisen bzw. regeln zu können ist eine kontinuierliche Überwachung der Biogasparameter (s. o.) mittels Onlineanalytik unverzichtbar.Around the quality of the product and the optimal operation of the biogas plant to be able to regulate is a continuous monitoring the biogas parameters (see above) are indispensable by means of online analytics.
Eine kontinuierliche Überwachung der Biogasparameter ist ebenfalls Voraussetzung für eine Einspeisung des Gasesgemisches in öffentliche oder industrielle Gasnetze.A continuous monitoring the biogas parameter is also a prerequisite for an infeed of the gas mixture in public or industrial gas networks.
Funktionsprinzip der neuen Biogas-MesstechnikWorking principle of the new Biogas Measurement
Alle heute üblichen Verfahren zur Messung von Biogasparametern sind sehr aufwändig und teuer, zu langsam, d. h. nicht an Zeitkonstante der Parameterschwankung angepasst oder aber nicht onlinefähig.All usual today Methods for measuring biogas parameters are very complex and expensive, too slow, d. H. not at the time constant of the parameter fluctuation adapted or not onlineable.
Die hier vorgeschlagene Messtechnik funktioniert dergestalt, dass ein optisches Spektrum der zu untersuchenden Probe nach einem chemometrischen Kalibrationsmodell ausgewertet wird. Abhängig von der Art und der Konzentration der im Biogas zu bestimmenden Gaskomponenten ist dafür der ultraviolette, der visuelle oder der infrarote Spektralbereich bzw. eine Kombination daraus zu verwenden.The here proposed measurement technology works such that a Optical spectrum of the sample to be examined after a chemometric Calibration model is evaluated. Depending on the type and concentration the gas components to be determined in the biogas is the ultraviolet, the visual or the infrared spectral range or a combination to use it.
Die Chemometrie ist ein mathematisch-statistisches Verfahren zur Extraktion physikalischer bzw. chemischer Informationen aus ein- und mehrdimensionalen Datensätzen.The Chemometry is a mathematical-statistical extraction method physical or chemical information from one- and multi-dimensional Records.
So ist beispielsweise die Reproduktion des Spektrums einer Reinsubstanz A aus einem Satz von A enthaltenden Gemisch-Spektren möglich, wenn in einem chemometrischen Verfahren anhand von Kalibrierspektren (Spektren von A in bekannter Konzentration enthaltenden Gemischen) ein Zusammenhang ermittelt wurde. So sind Vorhersagemodelle für die Konzentration von A in A enthaltenden Gemischen generierbar.So is, for example, the reproduction of the spectrum of a pure substance A possible from a set of A mixture spectra, if in a chemometric method based on calibration spectra (Spectra of mixtures containing A in known concentration) a connection has been identified. So are predictive models for concentration Generable from A in A containing mixtures.
Ebenso ist dieses Verfahren auf die Konzentrationsbestimmung von Substanzgruppen anwendbar sowie auf die Bestimmung physikochemischer und kolligativer Eigenschaften von Substanzgemischen.As well this method is based on the concentration determination of substance groups applicable as well as the determination of physicochemical and colligative Properties of substance mixtures.
Parallel und gleichzeitig sind damit alle Haupt- und Nebenkonzentrationen sowie daraus ableitbare Summenparameter oder physikalische Größen bestimmbar.Parallel and at the same time they are all major and minor concentrations as well as derivable sum parameters or physical quantities.
Es sind eine Reihe mathematischer Prozeduren zum Thema bekannt, beispielsweise die regularisierte Diskriminanzanalyse, (RDA), die Hauptkomponentenanalyse (PCR), die partially-least-squares-Methode (PLS) oder die multiple lineare Regression (MLR).It A number of mathematical procedures are known on the subject, for example the regularized discriminant analysis (RDA), the principal component analysis (PCR), the least-squares method (PLS) or the multiple linear regression (MLR).
Die Methode der Chemometrie ist in ihrer Anwendbarkeit nicht auf spektroskopische Daten beschränkt, spektroskopische Daten sind aber, wenn sie zur Charakterisierung von Stoff- oder Systemeigenschaften geeignet sind, besonders leicht und schnell zu generieren.The Method of chemometry is not applicable to spectroscopic applicability Data limited, however, spectroscopic data are available when used for characterization of fabric or system properties are particularly light and generate quickly.
Voraussetzung für den Einsatz von Spektroskopie ist eine hinreichende spektroskopische Repräsentation von Stoff- oder Gemischeigenschaften.requirement for the Use of spectroscopy is a sufficient spectroscopic representation of fabric or blend properties.
Vorgehensweise:Method:
Es werden chemometrische Kalibrationsmodelle für die Konzentrationen der Haupt- und Nebenkomponenten sowie für Summenparameter oder physikalische Größen von Biogasen erstellt.It chemometric calibration models for the concentrations of major and secondary components as well as for Summed parameters or physical quantities of biogases.
Von einem Teilstrom des Biogases wird in regelmäßigen Zeitintervallen ein Spektrum gemessen, welches nach o. g. Kalibrationsmodellen ausgewertet werden kann.From a partial stream of the biogas is a spectrum at regular time intervals measured, which after o. g. Calibration models are evaluated can.
Mit der oben genannten Vorrichtung lässt sich die Onlineanalyse von Biogasen solchermaßen durchführen, dassWith the above device can be perform the online analysis of biogases in such a way that
- 1. ein Teilstrom des Biogases mittele einer Pumpe kontinuierlich durch eine Gasküvette geleitet wird,1. a partial stream of biogas by means of a Pump is continuously passed through a gas cell,
- 2. von diesem Gasgemisch ein Spektrum mithilfe eines Spektrometers gemessen wird,2. from this mixed gas a spectrum using a spectrometer is measured
- 3. dieses Spektrum nach einem oder mehreren vorher erstellten chemometrischen Kalibrationsmodellen hinsichtlich der Konzentrationen der Haupt- und Nebenkomponenten sowie Summenparametern oder physikalischen Größen ausgewertet wird,3. this spectrum according to one or more previously prepared chemometric calibration models in terms of the concentrations of the major and minor components and sums parameters or physical quantities is evaluated,
- 4. Die Schritte 1 bis 3 werden automatisch von einem softwaregesteuerten Spektrometer durchgeführt.4. Steps 1 through 3 are automatically controlled by a software Spectrometer performed.
Die Eigenschaften und Vorteile, welche sich mit dieser Erfindung erzielen lassen:The features and benefits, which can be achieved with this invention:
- • Die neue Messtechnik ist sehr viel schneller und damit kostengünstiger als die DIN-Methoden• The new measurement technology is much faster and thus more cost-effective as the DIN methods
- • Die Messtechnik ist voll automatisierbar• The Measurement technology is fully automatable
- • Die Messtechnik ist onlinefähig• The Measurement technology is online
- • Durch die Flexibilität des Kalibrationsprinzips und des Spektralbereichs des eingesetzten Spektrometers ist die Messtechnik an viele Analysenprobleme anpassbar.• By the flexibility the calibration principle and the spectral range of the used Spectrometer is the measurement technology adaptable to many analysis problems.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200820003790 DE202008003790U1 (en) | 2008-03-18 | 2008-03-18 | Device for fast on-line measurement in biogas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200820003790 DE202008003790U1 (en) | 2008-03-18 | 2008-03-18 | Device for fast on-line measurement in biogas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE202008003790U1 true DE202008003790U1 (en) | 2008-05-15 |
Family
ID=39400341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE200820003790 Expired - Lifetime DE202008003790U1 (en) | 2008-03-18 | 2008-03-18 | Device for fast on-line measurement in biogas |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE202008003790U1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010031528B4 (en) * | 2010-07-19 | 2013-04-25 | Klaus Seeger | System for determining an energy content of a solid fuel and use of the system |
| CN109306321A (en) * | 2018-12-14 | 2019-02-05 | 黑龙江省能源环境研究院 | A kind of biogas fermentation environment on-line monitoring early warning system |
| CN109406800A (en) * | 2018-02-09 | 2019-03-01 | 北京华泰美景科技发展有限公司 | A kind of on-line automatic analysis system of coal-burning power plant's First air coal dust element |
| WO2020160880A1 (en) | 2019-02-07 | 2020-08-13 | IFP Energies Nouvelles | Method for measuring the concentration of gaseous species in a biogas |
| WO2021204450A1 (en) * | 2020-04-09 | 2021-10-14 | Sartorius Stedim Biotech Gmbh | Open-loop/closed-loop process control on the basis of a spectroscopic determination of undetermined substance concentrations |
-
2008
- 2008-03-18 DE DE200820003790 patent/DE202008003790U1/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010031528B4 (en) * | 2010-07-19 | 2013-04-25 | Klaus Seeger | System for determining an energy content of a solid fuel and use of the system |
| CN109406800A (en) * | 2018-02-09 | 2019-03-01 | 北京华泰美景科技发展有限公司 | A kind of on-line automatic analysis system of coal-burning power plant's First air coal dust element |
| CN109306321A (en) * | 2018-12-14 | 2019-02-05 | 黑龙江省能源环境研究院 | A kind of biogas fermentation environment on-line monitoring early warning system |
| WO2020160880A1 (en) | 2019-02-07 | 2020-08-13 | IFP Energies Nouvelles | Method for measuring the concentration of gaseous species in a biogas |
| FR3092665A1 (en) | 2019-02-07 | 2020-08-14 | IFP Energies Nouvelles | METHOD FOR MEASURING THE CONCENTRATION OF GASEOUS SPECIES IN A BIOGAS |
| WO2021204450A1 (en) * | 2020-04-09 | 2021-10-14 | Sartorius Stedim Biotech Gmbh | Open-loop/closed-loop process control on the basis of a spectroscopic determination of undetermined substance concentrations |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE202008003790U1 (en) | Device for fast on-line measurement in biogas | |
| DE102011007011A1 (en) | Analyzer for the automated determination of a measured variable of a liquid sample | |
| DE102009028067B3 (en) | Device and method for the spectrometric analysis of a beverage | |
| DE102016121226A1 (en) | A method for determining properties of a hydrocarbon-containing gas mixture and apparatus therefor | |
| DE10392663T5 (en) | A photo-acoustic detection method for measuring the concentration of non-hydrocarbon components of a methane-containing gas mixture | |
| DE3223167C2 (en) | Method for examining water containing decomposable carbon compounds | |
| DE102010039275B4 (en) | Method and apparatus for the online determination of the isotopic ratio of chlorine, bromine or sulfur in an organic sample | |
| DE19830720C1 (en) | Indirect method of measuring calorific value, heating value and water content of liquid waste specimens | |
| DE102009017932B4 (en) | A method for the continuous quantitative determination of an oxidizable chemical compound in an assay medium | |
| DE202011051637U1 (en) | Arrangement for the treatment of liquids, in particular for water treatment | |
| CN205643150U (en) | COD short -term test appearance | |
| DE102018131060A1 (en) | Method for operating an automatic analyzer | |
| WO2006089773A2 (en) | Method and device for determining the concentration of organically bound halogens | |
| DE102015122506A1 (en) | Method and device for determining a proportion of an element in a sample | |
| WO2022199928A1 (en) | Online or in situ measuring device for measuring the concentration of a gas | |
| DE2950261A1 (en) | METHOD AND DEVICE FOR MONITORING CHEMICAL PROCESSES | |
| DE19515561C2 (en) | Method for the determination of hydrocarbons | |
| DE102018131061A1 (en) | Method of diluting a sample liquid and dilution unit for subsequent analysis | |
| DE102007054157A1 (en) | Gas/gas mixture analyzing device for use in beverage and foodstuffs industry, has gas line connected with another gas line using bypass line that branches-off from former gas line at branching point, where valve is arranged in bypass line | |
| RU2774152C1 (en) | Method for determining polyorganosiloxanes by means of high-resolution atomic absorption spectrometry with a continuous spectral source in the mode of electrothermal sample atomisation | |
| DE10132390B4 (en) | Apparatus and method for analyzing organic substances of pure or ultrapure water | |
| DE102006031040A1 (en) | Mercury measuring method for use during e.g. waste incineration, involves splitting mercury compounds to obtain atomic mercury, whose concentration is measured by photometer, where gas comes into contact with boron compounds | |
| EP4230588A1 (en) | Method and device for the continuous, at least partial removal of foreign matter from a fluid, in particular in waste water | |
| DE10256009B4 (en) | Method and apparatus for providing a gaseous substance for the analysis of chemical elements or compounds | |
| DE202018004620U1 (en) | Apparatus for rapid discrimination of explosives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R086 | Non-binding declaration of licensing interest | ||
| R207 | Utility model specification |
Effective date: 20080619 |
|
| R150 | Term of protection extended to 6 years | ||
| R150 | Term of protection extended to 6 years |
Effective date: 20111026 |
|
| R157 | Lapse of ip right after 6 years | ||
| R157 | Lapse of ip right after 6 years |
Effective date: 20141001 |