EP0572848B1 - Verfahren zur Bestimmung des Endpunktes für den Frischprozess in Sauerstoffkonvertern - Google Patents
Verfahren zur Bestimmung des Endpunktes für den Frischprozess in Sauerstoffkonvertern Download PDFInfo
- Publication number
- EP0572848B1 EP0572848B1 EP93107946A EP93107946A EP0572848B1 EP 0572848 B1 EP0572848 B1 EP 0572848B1 EP 93107946 A EP93107946 A EP 93107946A EP 93107946 A EP93107946 A EP 93107946A EP 0572848 B1 EP0572848 B1 EP 0572848B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxygen
- converter
- computer
- supply
- vol
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
Definitions
- the invention relates to a method for determining the End point for the fresh process in oxygen converters at the Steelmaking.
- the mass spectrometric analysis of the exhaust gas components is on known from steel and iron, 1972, pages 1278 to 1283 and DE-A-2 839 316.
- the known processes are concerned it is an attempt to make statements in a dynamic process to get about the respective state of the molten steel.
- sublance technique is dynamic methods. Here one or two samples are taken shortly before the end of the blowing the insertion of a lance in the blowing position. The carbon content is determined by a quick determination using a dependency determined from the solidification temperature.
- the disadvantages of sublance technology are the very high investment and maintenance costs as well as an unsatisfactory hit rate in Terms of carbon content.
- a method is described there in which the monitoring or measurement using a mass spectrometer and Flow meter the amount of decarburization of the melted Steel is determined.
- the concentration measurement of e.g. CO and CO2 via the exhaust gas analysis and the determination of the exhaust gas rate gives the decarburization rate.
- From the product of decarburization rate and the measuring time interval gives the amount of carbon removed, and a further summation of the amounts of carbon
- the total amount of gasified carbon supplies over the freshness period.
- a balance between the introduced and the distributed Carbon gives the final amount of carbon.
- the invention is therefore based on the object of a method of the type mentioned in such a way that individually for each melt as early as possible and at a certain one Bad carbon content by switching off the oxygen supply can be decided when fresh.
- the course over time a number of exhaust gas components by mass spectrometry determined.
- the sinks Share of individual exhaust gas components, while share of others Exhaust components increase.
- the parameters are chosen so that they are significant Show change when the exhaust gas components are slow rise or fall.
- the measured exhaust gas values are digitized as analog values with an analog-digital converter and by means of the computer program the derived parameters are formed from the digital values obtained.
- Measuring point for measuring point which are approximately 3 seconds apart, is scanned and the respective time change is compared with a target state.
- This target state means, for example, "fall” with CO, while it means “rise” with nitrogen. If the scanning, ie the comparison of the temporal change of the measuring points with the respective target state in several runs in succession, the same tendency (CO falls constantly, N 2 rises continuously), a signal is generated which is used to switch off the oxygen supply.
- the number of comparison runs (loops) is previously fixed and is 2 to 10, preferably 7.
- the pattern recognition is only started when a point has been reached in the course of time from which the final drop occurs of the CO content or the final increase in the N 2 content can be expected. This is roughly determined, for example, using one of the static models given above.
- carbon is blown into the batch through the bottom of the converter. If there is enough carbon in the melt, the supply of carbon is stopped while freshening continues.
- the pattern recognition process is then 5 minutes, for example. started after the coal stop, that is, when it is approximately certain that only a little carbon can react with oxygen, the carbon monoxide content in the exhaust gas stream thus begins to decrease steadily.
- the computer generates a signal that either in DDC mode (Dynamic Digital Control) the oxygen supply ended independently or sent to the converter control center is where the oxygen supply is then terminated by the operating personnel can be.
- DDC mode Dynamic Digital Control
- This second alternative has the advantage that the operating personnel the oxygen supply based on experience still a little bit maintained despite the signal can.
- a converter 1 is shown schematically in FIG. 1.
- the Oxygen blowing device is for reasons of clarity omitted.
- Above the converter opening 2 is in one close distance 4 to an exhaust hood 3, through which the exhaust gases get into the chimney 5 from the converter 1.
- the suction pumps are also not shown for reasons of clarity.
- a schematically illustrated branch 6 is supplied from the chimney 5 a mass spectrometer 7 with those to be analyzed Exhaust components.
- the measurement signals are, for example, with With the help of a pen 8 plotted over time.
- the analog values are scanned and fed to an analog-digital converter 9.
- the digitized values arrive in the computer 10 and are processed further there. After being found is the right time to turn off the oxygen supply is reached, a signal is generated by the computer 10, that in the present example via the digital output 11 to converter control station, not shown, is transmitted.
- the procedure is based on feeling the above time-varying sizes.
- This requires a computer program to create, as shown schematically in Fig. 5 and convert the analog values into digital data.
- the computer program first generates the derived quantities and constantly compares the change over time with the target state.
- the mass spectrometer is completely exposed to nitrogen. If the measurement now begins, ie if the exhaust gases to be examined are fed to the mass spectrometer, the proportion of calibration gas nitrogen in the mass spectrometer drops. If it drops below 95%, the program is deactivated by a reset. Are the 5 min. Once the carbon supply has been reached, a query is made again as to whether the calibration gas portion of the mass spectrometer has dropped to below 95%. If this question is answered in the affirmative, the counter in the program is set to 0 and the first condition is queried. In this case the condition is "the nitrogen content increases”. If the answer is no, the run is restarted.
- the second condition is queried, in this case "the carbon dioxide content increases”. If the answer is no, the run is restarted, if the answer is yes, the third condition is queried, in this case "the carbon monoxide content drops”. If the answer is no, the system restarts. Otherwise, other conditions are taken into account, e.g. B. falls over time the ratio of CO to N 2 . Another condition could be whether the gradient of the falling edge of this ratio (CO / N 2 ) exceeds a certain value. If all conditions are met, the counter is increased by one and the conditions are queried for the next measuring point. If the number of loops reaches a previously set value, the process is ended and the signal to switch off the oxygen supply is generated.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
Description
- zu Beginn der Messung das Massenspektrometer mit 100 Vol-% Stickstoff beaufschlagt wird und mit der Endpunktbestimmung begonnen wird, wenn der CO-Anteil über 40 Vol-% und der Stickstoffanteil unter 40 Vol-% liegt;
- die Bedingungen (pro Zeit)
- a) Stickstoffgehalt steigt und
- b) Kohlendioxid steigt und
- c) das Verhältnis CO/N2 fällt oder der Wert (CO/N2) CO[100 - N2]/100 fällt
- Fig. 1
- den prinzipiellen Aufbau der Meß- und Auswerteapparatur am Konverter,
- Fig. 2
- den zeitlichen Verlauf der Volumenanteile von CO, CO2 und N2,
- Fig. 3
- den zeitlichen Verlauf des Verhältnisses von CO und N2 multipliziert mit dem Konvertergasanteil,
- Fig. 4
- den zeitlichen Verlauf des Verhältnisses von CO und N2 und
- Fig. 5
- ein Flußdiagramm des erfindungsgemäßen Auswerteververfahrens.
Claims (4)
- Verfahren zur Bestimmung des Endpunktes für den Frischprozeß in Sauerstoffkonvertern bei der Stahlerzeugung, bei dem während des Frischens fortlaufend die aus dem Konverter entweichenden Abgasbestandteile CO und CO2 und N2 massenspektrometrisch bestimmt werden, wobei:erfüllt sein müssen und mit Hilfe eines Rechnerprogramms fortlaufend mit einer Sollkurve verglichen werden, und daß erst, wenn diese Bedingungen nach zwei bis zehn aufeinanderfolgenden Vergleichsdurchläufen vom Rechner als erfüllt erkannt worden sind, die Sauerstoffzufuhr beendet wird.zu Beginn der Messung das Massenspektrometer mit 100 Vol-% Stickstoff beaufschlagt wird und mit der Endpunktbestimmung begonnen wird, wenn der CO-Anteil über 40 Vol-% und der Stickstoffanteil unter 40 Vol-% liegt;die Bedingungen (pro Zeit)a) Stickstoffgehalt steigt undb) Kohlendioxid steigt undc) das Verhältnis CO/N2 fällt oder der Wert (CO/N2) CO[100 - N2]/100 fällt
- Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß die gemessenen Werte Analogwerte sind, die digitalisiert werden und dann dem Rechner zugeführt werden. - Verfahren nach Anspruch 2
dadurch gekennzeichnet, daß der Rechner im Dynamic Digital Control Modus (DDC-Modus) die Sauerstoffzufuhr selbständig beendet. - Verfahren nach Anspruch 2,
dadurch gekennzeichnet,
daß der Rechner das Signal zur Beendigung der Sauerstoffzufuhr über einen digitalen Ausgang zum Konverterleitstand sendet, wo dann die Sauerstoffzufuhr abgeschaltet wird.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4217933A DE4217933C2 (de) | 1992-05-30 | 1992-05-30 | Verfahren zur Bestimmung des Endpunktes für den Frischprozeß in Sauerstoffkonvertern |
| DE4217933 | 1992-05-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0572848A2 EP0572848A2 (de) | 1993-12-08 |
| EP0572848A3 EP0572848A3 (en) | 1994-08-10 |
| EP0572848B1 true EP0572848B1 (de) | 1998-07-08 |
Family
ID=6460082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93107946A Expired - Lifetime EP0572848B1 (de) | 1992-05-30 | 1993-05-15 | Verfahren zur Bestimmung des Endpunktes für den Frischprozess in Sauerstoffkonvertern |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0572848B1 (de) |
| AT (1) | ATE168137T1 (de) |
| DE (2) | DE4217933C2 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2837193C2 (ru) * | 2023-02-13 | 2025-03-26 | ООО "МегалТЭК" | Способ управления плавкой при производстве стали в дуговой сталеплавильной печи |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2154282T3 (es) * | 1993-06-15 | 2001-04-01 | Mannesmann Ag | Procedimiento para la produccion de acero con bajo contenido en fosforo. |
| DE4412236C2 (de) * | 1993-06-15 | 1998-04-16 | Mannesmann Ag | Verfahren zur Herstellung von Stahl mit niedrigem Phosphorgehalt |
| DE10346768A1 (de) | 2003-10-06 | 2005-04-21 | Zimmer Ag | Verfahren zur automatischen Analyse von polymerhaltigem Abfall und Analyseautomat hierzu |
| DE10346769A1 (de) * | 2003-10-06 | 2005-04-21 | Zimmer Ag | Analyseautomat und Verfahren zur Überwachung der Polymerherstellung mittels Massenspektroskopie |
| DE102006050888A1 (de) * | 2006-10-27 | 2008-04-30 | Siemens Ag | Verfahren zur Regelung des Kohlenmonoxid-Austrags bei einem metallurgischen Schmelzverfahren |
| DE102009060258A1 (de) * | 2009-12-23 | 2011-06-30 | SMS Siemag Aktiengesellschaft, 40237 | Steuerung des Konverterprozesses durch Abgassignale |
| RU2652663C2 (ru) * | 2015-11-27 | 2018-04-28 | Общество Ограниченной Ответственности "Научно-производственное объединение "Санкт-Петербургская электротехническая компания" | Способ управления процессом продувки конвертерной плавки с использованием информации отходящих газов |
| CN113388712B (zh) * | 2021-06-15 | 2022-04-05 | 马鞍山钢铁股份有限公司 | 一种低碳lf炉工艺钢转炉冶炼方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR7805395A (pt) * | 1977-08-22 | 1979-05-02 | Kobe Steel Ltd | Processo para controle de sopramento em conversor |
| JPS5442323A (en) * | 1977-09-10 | 1979-04-04 | Nisshin Steel Co Ltd | Control procedure of steel making process using mass spectormeter |
| DE2835548C2 (de) * | 1978-08-14 | 1983-10-20 | Klöckner-Werke AG, 4100 Duisburg | Verfahren zum Bestimmen des Gehaltes einer Charge eines metallurgischen Systems an einem oder mehreren Elementen |
-
1992
- 1992-05-30 DE DE4217933A patent/DE4217933C2/de not_active Expired - Lifetime
-
1993
- 1993-05-15 EP EP93107946A patent/EP0572848B1/de not_active Expired - Lifetime
- 1993-05-15 AT AT93107946T patent/ATE168137T1/de not_active IP Right Cessation
- 1993-05-15 DE DE59308730T patent/DE59308730D1/de not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2837193C2 (ru) * | 2023-02-13 | 2025-03-26 | ООО "МегалТЭК" | Способ управления плавкой при производстве стали в дуговой сталеплавильной печи |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0572848A3 (en) | 1994-08-10 |
| ATE168137T1 (de) | 1998-07-15 |
| DE4217933C2 (de) | 1995-03-23 |
| DE4217933A1 (de) | 1993-12-02 |
| DE59308730D1 (de) | 1998-08-13 |
| EP0572848A2 (de) | 1993-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1433443B2 (de) | Verfahren zur ueberwachung und regelung der sauerstoffauf blasverfahren | |
| DE4217933C2 (de) | Verfahren zur Bestimmung des Endpunktes für den Frischprozeß in Sauerstoffkonvertern | |
| DE2839315C2 (de) | Verfahren zur Steuerung der Stahlherstellung | |
| DE2707502C2 (de) | Verfahren zum Steuern der Temperatur und des Kohlenstoffgehalts einer Stahlschmelze in einem Sauerstoffblaskonverter | |
| EP1310573B1 (de) | Verfahren zur Herstellung einer Metallschmelze an Hand eines dynamischen Prozessmodells, inklusiv Korrekturmodell | |
| DE2755587C2 (de) | Einrichtung zur Schnellbestimmung der Bindungsformen von Gasen, wie Sauerstoff oder Stickstoff in festen oder flüssigen kleinen Metallproben | |
| DE2109676A1 (de) | Verfahren zur dynamisch geregelten Entkohlung von Stahlschmelzen | |
| EP4073277A1 (de) | Verfahren zur bestimmung und steuerung oder regelung des phosphor-gehaltes in einer metallischen schmelze während eines frischprozesses einer metallischen schmelze in einem metallurgischen reaktor | |
| DE1508245C3 (de) | Verfahren zur Steuerung des Kohlenstoffgehaltes in geschmolzenem Stahl während des Sauerstoffaufblasverfahrens | |
| DE3025425C2 (de) | Verfahren und Vorrichtung zur Steuerung der Vakuumentgasung einer Stahlschmelze | |
| DE2836694C2 (de) | Verfahren zum Überwachen des Endpunktes beim Frischen von kohlenstoffarmem Stahl im Sauerstoffkonverter | |
| DE1965073C3 (de) | Verfahren zur kontinuierlichen Bestimmung des Kohlenstoffgehaltes der Stahlschmelze in einem Sauerstoff-Aufblaskonverter | |
| EP0281504B1 (de) | Verfahren und Vorrichtung zur Entgasungsbehandlung einer Stahlschmelze in einer Vakuumanlage | |
| DD298417A5 (de) | Prozessregelungssystem fuer die herstellung von russ | |
| AT406587B (de) | Verfahren zum bestimmen des blaseendes während des frischens einer stahlschmelze in einem konverter | |
| DE2657540A1 (de) | Verfahren zur steuerung von abgasen in einem sauerstoffblaskonverter | |
| EP4461827A1 (de) | Verfahren zum betreiben eines anlagenverbunds | |
| DE19617384A1 (de) | Anordnung und Verfahren zur Regelung des Mischungsverhältnisses zweier Gasvolumenströme durch eine Venturi-Düse über deren Düsennadel | |
| WO2024199973A1 (de) | Verfahren zum betreiben eines anlagenverbunds | |
| DE1458827C2 (de) | Verfahren zur automatischen Steuerung und Regelung des Prozeßablaufs beim Sauerstoffaufblasverfahren | |
| AT259597B (de) | Verfahren und Vorrichtung zur kontinuierlichen Bestimmung des jeweiligen Kohlenstoffgehaltes von Metallschmelzen beim pneumatischen Frischen im Konverter | |
| EP0856146A2 (de) | Verfahren zur bestimmung von gasvolumenströmen in prozessen der flüssigphase in einem elektroofen | |
| DE1433701C (de) | Verfahren zur Ermittlung des Zeitpunktes für die Unterbrechung des Sauerstoffblasens bei einem Sauerstoffaufblaskonverter | |
| WO2024223670A1 (de) | Betriebsverfahren für eine hüttentechnische anlage der eisen- oder stahlerzeugung | |
| WO2004072309A2 (de) | Multivariate, prädiktive regelung eines direktreduktionsprozesses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19930515 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19960423 |
|
| RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: GEORGSMARIENHUETTE GMBH |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980708 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 19980708 Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980708 Ref country code: GB Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980708 Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980708 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19980708 |
|
| REF | Corresponds to: |
Ref document number: 168137 Country of ref document: AT Date of ref document: 19980715 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REF | Corresponds to: |
Ref document number: 59308730 Country of ref document: DE Date of ref document: 19980813 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19981008 |
|
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| EN | Fr: translation not filed | ||
| GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 19980708 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990515 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990515 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990531 |
|
| 26N | No opposition filed | ||
| BERE | Be: lapsed |
Owner name: GEORGSMARIENHUTTE G.M.B.H. Effective date: 19990531 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20120702 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59308730 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130516 |