EP0212611A2 - Coke dry quenching chamber - Google Patents
Coke dry quenching chamber Download PDFInfo
- Publication number
- EP0212611A2 EP0212611A2 EP86111408A EP86111408A EP0212611A2 EP 0212611 A2 EP0212611 A2 EP 0212611A2 EP 86111408 A EP86111408 A EP 86111408A EP 86111408 A EP86111408 A EP 86111408A EP 0212611 A2 EP0212611 A2 EP 0212611A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- walls
- cooling
- coke
- cooling chamber
- conductive material
- 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.)
- Granted
Links
- 239000000571 coke Substances 0.000 title claims abstract description 30
- 238000010791 quenching Methods 0.000 title 1
- 230000000171 quenching effect Effects 0.000 title 1
- 238000001816 cooling Methods 0.000 claims abstract description 56
- 239000004020 conductor Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 238000010276 construction Methods 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002347 wear-protection layer Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B39/00—Cooling or quenching coke
- C10B39/02—Dry cooling outside the oven
Definitions
- the invention relates to a dry coke cooling chamber with vertical outer walls designed as cooling walls and parallel vertical cooling walls arranged in the cooling chamber and supporting walls running transversely thereto.
- the object of the invention is to propose a construction in which wear on the pipes is completely avoided without a substantial loss of thermal conductivity and, even after years of operation, it is not necessary to replace the pipes.
- the invention provides that the cooling walls and / or the support walls become narrower towards the bottom and the approximately rectangular coke cooling shafts formed by the cooling and support walls expand downwards.
- This conical design of the cooling or supporting walls in the cooling chamber considerably reduces the lateral pressure on the walls and when the hot coke pieces slide past these walls, the abrasion is also significantly reduced.
- the wear rate in the previous version is approximately 0.4 mm / year, it can be reduced to approximately half as a result of a taper as specified in claim 3. It is particularly advantageous if the expansion of the coke cooling shaft is carried out continuously downwards, so that as far as possible no irregularities occur during the movement of the coke along the walls and therefore no places with much higher wear occur.
- the invention further provides that flat, exchangeable wear plates are arranged on the outside of the membrane tube walls and the space between the wear plates and the tubes or webs is filled with highly thermally conductive material.
- the cooling walls in the cooling chamber are arranged vertically and completely flat, so that the hot coke can slide down the walls without any significant abrasion.
- the wear plates made of metallic materials anyway have a high thermal conductivity and the space between the wear plates and the tubes, in particular in the area of the webs between the individual tubes, is e.g. B. not filled with a heat-insulating layer of air, but with highly thermally conductive material. It has surprisingly been found that despite a slight reduction in the heat exchange surface and despite an increase in the effective wall thickness to be penetrated by the heat, the heat transfer to the cooling medium to be heated in the pipes is not significantly deteriorated.
- graphite or diabon or heat-conductive concrete is proposed as the highly thermally conductive material.
- the thermal conductivity is sometimes over 100 watts / m and Kelvin.
- compacted or pressed and / or coke breeze or dust and / or graphite dust provided with binder can also be used.
- the latter materials have the advantage that they are partly products of the coking plant and are therefore inexpensive. These materials can be pressed into place in the remaining gaps after installation of the pipes and wear plates or used as prefabricated elements.
- the wear plates on both sides of the membrane tube walls are advantageously connected to one another by means of screws and / or tie rods and are held in front of the tubes. If necessary, individual wear plates can also be replaced.
- the wear plates are arranged completely separate from the cooling pipes, they can be given a certain conicity in the flow direction of the hot coke. This can be achieved in that the wear plate distance in the upper area of the membrane tube walls is larger than in the lower area.
- the use of the wear plates in connection with the highly thermally conductive intermediate layer also has the economic advantage that the pressure-carrying pipeline system no longer has to be designed taking into account the possible wear. This version therefore no longer requires pipes of considerable wall thickness. In addition, there is no high proportion of welds with a large cross-section.
- both the support walls (3) and the cooling walls (5) have a rounded wear layer on their top.
- the upper edge can also be an approximately flat surface (14) on which coke pieces are deposited as a certain wear protection layer.
- the lateral vertical wear plates (10) protrude upwards with the wear edge (15).
- FIGS. 3 to 5 show the known arrangement of support and cooling walls (3) and (5) in the cooling chamber.
- the wear plates (10) are arranged on the sides of the cooling walls (5) in contact with the coke and are held in front of the pipes or the highly thermally conductive material (11) by means of fastening elements (13) guided through the webs (12).
- the layer of highly thermally conductive material arranged between the tubes and the wear plates can have different thicknesses, ie. H. the thickness decreases from top to bottom.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Coke Industry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
Description
Die Erfindung betrifft eine Kokstrockenkühlkammer mit als Kühlwände ausgebildeten senkrechten Außenwänden und in der Kühlkammer angeordneten parallelen senkrechten Kühlwänden und quer dazu verlaufenden Stützwänden.The invention relates to a dry coke cooling chamber with vertical outer walls designed as cooling walls and parallel vertical cooling walls arranged in the cooling chamber and supporting walls running transversely thereto.
Derartige Kokstrockenkühlkammern sind in "Technischen Mitteilungen", Heft 9/1982, Seiten 434 bis 439 ausführlich beschrieben. Bild 3 auf Seite 435 zeigt die Anordnung der Kühlwände im Koksschacht, wobei die sogenannten Membranrohrwände aus senkrecht und parallel zueinander angeordneten Rohrreihen bestehen, die jeweils über Stege miteinander verbunden sind. Zur Erreichung eines guten wärmeübergangs von dem heißen Koks an das Kühlmedium in den Rohren sind dabei die Rohre unverkleidet. Es hat sich nun gezeigt, daß bei einem jahrelangen Dauerbetrieb der Kokstrockenkühlkammer es zu einem gewissen Verschleiß an den Rohrwänden kommt, so daß im Extremfall die Rohrwände ausgetauscht werden müssen.Such coke-drying cooling chambers are described in detail in "Technische Mitteilungen",
Aufgabe der Erfindung ist es, eine Konstruktion vorzuschlagen, bei der ohne wesentlichen Verlust der Wärmeleitfähigkeit ein Verschleiß an den Rohren gänzlich vermieden wird und wobei auch nach jahrelangem Betrieb ein Auswechseln der Rohre nicht erforderlich ist.The object of the invention is to propose a construction in which wear on the pipes is completely avoided without a substantial loss of thermal conductivity and, even after years of operation, it is not necessary to replace the pipes.
Zur Lösung dieser Aufgabe sieht die Erfindung vor, daß die Kühlwände und/oder die Stützwände nach unten hin schmaler werden und die von den Kühl- und Stützwänden gebildeten, etwa rechteckigen Kokskühlschächte sich nach unten hin erweitern. Durch diese konische Ausführung der KÜhl- bzw. Stützwände in der Kühlkammer wird der seitliche Druck auf die Wände erheblich verringert und beim Herabgleiten der heißen Koksstücke an diesen Wänden vorbei wird auch der Abrieb entscheidend verringert. Während bei der bisherigen Ausführung die Verschleißrate bei ca. 0,4 mm/Jahr liegt, so kann sie in Folge einer Konizität, wie sie im Anspruch 3 angegeben ist, auf etwa die Hälfte reduziert werden. Dabei ist es insbesondere günstig, wenn die Erweiterung der Kokskühlschächtc nach unten hin stufenlos erfolgt, so daß möglichst keine Unregelmäßigkeiten während der Bewegung des Kokses an den Wänden entlang entstehen und von daher keine Stellen mit wesentlich höherem Verschleiß auftreten.To achieve this object, the invention provides that the cooling walls and / or the support walls become narrower towards the bottom and the approximately rectangular coke cooling shafts formed by the cooling and support walls expand downwards. This conical design of the cooling or supporting walls in the cooling chamber considerably reduces the lateral pressure on the walls and when the hot coke pieces slide past these walls, the abrasion is also significantly reduced. While the wear rate in the previous version is approximately 0.4 mm / year, it can be reduced to approximately half as a result of a taper as specified in
Die Erfindung sieht weiterhin vor, daß an den Membranrohrwänden außen ebene, auswechselbare Verschleißplatten angeordnet sind und der Zwischenraum zwischen den Verschleißplatten und den Rohren bzw. Stegen mit hochwärmeleitfähigem Material ausgefüllt ist. Bei dieser Ausführung sind die Kühlwände in der Kühlkammer senkrecht und völlig eben angeordnet, so daß der heiße Koks ohne nennenswerten Abrieb von oben nach unten an den Wänden herabgleiten kann. Die aus metallischen Materialien bestehenden Verschleißplatten besitzen ohnehin eine hohe Wärmeleitfähigkeit und der Zwischenraum zwischen den Verschleißplatten und den Rohren, insbesondere in dem Bereich der Stege zwischen den einzelnen Rohren, ist z. B. nicht mit einer wärmeisolierenden Luftschicht, sondern mit hochwärmeleitfähigem Material ausgefüllt. Es hat sich überraschenderweise gezeigt, daß trotz geringfügiger Verringerung der Wärmeaustauschfläche und trotz Vergrößerung der effektiven, von der Wärme zu durchdringenden Wandstärke der Wärmeübergang an das aufzuheizende Kühlmedium in den Rohren nicht nennenswert verschlechtert wird.The invention further provides that flat, exchangeable wear plates are arranged on the outside of the membrane tube walls and the space between the wear plates and the tubes or webs is filled with highly thermally conductive material. In this embodiment, the cooling walls in the cooling chamber are arranged vertically and completely flat, so that the hot coke can slide down the walls without any significant abrasion. The wear plates made of metallic materials anyway have a high thermal conductivity and the space between the wear plates and the tubes, in particular in the area of the webs between the individual tubes, is e.g. B. not filled with a heat-insulating layer of air, but with highly thermally conductive material. It has surprisingly been found that despite a slight reduction in the heat exchange surface and despite an increase in the effective wall thickness to be penetrated by the heat, the heat transfer to the cooling medium to be heated in the pipes is not significantly deteriorated.
Als hochwärrneleitfähiges Material wird erfindungsgemäß Graphit bzw. Diabon oder warmeleitfahiger Beton vorgeschlagen. Dabei beträgt die Wärmeleitfähigkeit teilweise über 100 Watt/ m und Kelvin. Es kann aber auch verdichteter bzw. gepreßter und/oder mit Bindemittel versehener Koksgrus bzw. -staub und/ oder Graphitstaub verwendet werden. Die letzteren Materialien haben den Vorteil, daß sie teilweise Produkte der Kokerei sind und von daher preiswert zu haben sind. Diese Materialien können an Ort und Stelle nach Montage der Rohre und der Verschleieplatten in die verbleibenden Zwischenräume eingepreßt oder als vorgefertigte Elemente eingesetzt werden.According to the invention, graphite or diabon or heat-conductive concrete is proposed as the highly thermally conductive material. The thermal conductivity is sometimes over 100 watts / m and Kelvin. However, compacted or pressed and / or coke breeze or dust and / or graphite dust provided with binder can also be used. The latter materials have the advantage that they are partly products of the coking plant and are therefore inexpensive. These materials can be pressed into place in the remaining gaps after installation of the pipes and wear plates or used as prefabricated elements.
Die Verschleißplatten an beiden Seiten der Membranrohrwände werden günstigerweise über Schrauben und/oder Zuganker miteinander verbunden und vor den Rohren festgehalten. Im Bedarfsfall können dann auch einzelne Verschleißplatten ausgewechselt werden.The wear plates on both sides of the membrane tube walls are advantageously connected to one another by means of screws and / or tie rods and are held in front of the tubes. If necessary, individual wear plates can also be replaced.
Da die Verschleißplatten völlig von den Kühlrohren getrennt angeordnet sind, kann ihnen eine gewisse Konizität in Flusrichtung des heißen Kokses vorgegeben werden. Dies kann dadurch erreicht werden, daß der Verschleißplattenabstand im oberen Bereich der Membranrohrwande größer ist als im unteren. Die Verwendung der Verschleißplatten in Verbindung mit der hochwärmeleitfähigen Zwischenlage hat aber auch den wirtschaftlichen Vorteil, daß das druckführende Rohrleitungasystem nicht mehr unter Berücksichtigung des möglichen Verschleißes ausgelegt werden muß. Diese Ausführung benötigt'also nicht mehr Rohre von erheblicher Wanddicke. Darüber hinaus entfällt ein hoher Anteil von Schweißnähten mit großem Querschnitt.Since the wear plates are arranged completely separate from the cooling pipes, they can be given a certain conicity in the flow direction of the hot coke. This can be achieved in that the wear plate distance in the upper area of the membrane tube walls is larger than in the lower area. However, the use of the wear plates in connection with the highly thermally conductive intermediate layer also has the economic advantage that the pressure-carrying pipeline system no longer has to be designed taking into account the possible wear. This version therefore no longer requires pipes of considerable wall thickness. In addition, there is no high proportion of welds with a large cross-section.
Die Erfindung wird anhand der beigefügten Figuren 1 bis 5 beispielsweise näher erläutert.
Figur 1 zeigt schematisch einen Teil der Kühlkammer im senkrechten Schnitt.Figur 2 ist ein waagerechter Schnitt zuFigur 1.Figur 3 zeigt im senkrechten Schnitt Ausschnitte der Membranrohrwände.Figur 4 ist ein Schnitt nach der Linie A-A vonFigur 3.Figur 5 ist ein Schnitt nach der Linie B-B vonFigur 3.
- Figure 1 shows schematically a part of the cooling chamber in vertical section.
- Figure 2 is a horizontal section to Figure 1.
- Figure 3 shows in vertical section sections of the membrane tube walls.
- Figure 4 is a section along the line AA of Figure 3.
- Figure 5 is a section along the line BB of Figure 3.
In der schematischen Darstellung nach Figur 1 ist der obere Teil einer Kühlkammer dargestellt mit der Einfüllöffnung (1) und den äußeren Wänden (2) sowie den inneren Stützwänden (3). Rechtwinklig zu den Stützwänden (3) verlaufen die inneren Kühlwände (5), wobei die Oberkante der Kühlwände (5) in Figur 1 mit (14) bezeichnet ist. Zum Schutz vor dem von oben eingefüllten heißen Koks besitzen sowohl die Stützwände (3) als auch die Kühlwände (5) an ihrer Oberseite eine abgerundete Verschleißschicht. Wie in der Figur 3 angedeutet, kann die Oberkante auch eine etwa ebene Fläche (14) sein, auf der sich als gewisse Verschleißschutzschicht Koksstücke ablagern. Gleichzeitig stehen dabei die seitlichen senkrechten Verschleißplatten (10) nach oben mit der Verschleißkante (15) über.In the schematic representation of Figure 1, the upper part of a cooling chamber is shown with the fill opening (1) and the outer walls (2) and the inner support walls (3). The inner cooling walls (5) run at right angles to the supporting walls (3), the upper edge of the cooling walls (5) being designated by (14) in FIG. 1. To protect against the hot coke filled in from above, both the support walls (3) and the cooling walls (5) have a rounded wear layer on their top. As indicated in FIG. 3, the upper edge can also be an approximately flat surface (14) on which coke pieces are deposited as a certain wear protection layer. At the same time, the lateral vertical wear plates (10) protrude upwards with the wear edge (15).
Aus der Figur 1 ist weiterhin die Konizität der Außen- und Innenwände der Kühlkammer mit Erweiterung der Kokskühlschächte (6) nach unten hin ersichtlich. Figur 2 zeigt die an sich bekannte Anordnung von Stütz- und Kühlwänden (3) und (5) in der Kühlkammer. Aus den Figuren 3 bis 5 ist der Aufbau der einzelnen Membranrohrkühlwände (5) mit unterem Kühlmittelverteiler (7), den Kühlrohren (8) sowie dem Sammler (9) beschrieben. An den koksberührten Seiten der Kühlwände (5) sind die Verschleißplatten (10) angeordnet, die über durch die Stege (12) geführte Befestigungselemente (13) vor den Rohren bzw. dem hochwärmeleitfähigen Material (11) gehalten werden. Zur Erreichung der erfindungsgemäßen Konizität kann die zwischen den Rohren und den Verschleißplatten angeordnete Schicht aus hochwärmeleitfähigem Material verschieden dick sein, d. h. die Dicke nimmt von oben nach unten hin ab.From Figure 1, the taper of the outer and inner walls of the cooling chamber with expansion of the coke cooling shafts (6) downward can be seen. Figure 2 shows the known arrangement of support and cooling walls (3) and (5) in the cooling chamber. The structure of the individual membrane tube cooling walls (5) with the lower coolant distributor (7), the cooling tubes (8) and the collector (9) is described in FIGS. 3 to 5. The wear plates (10) are arranged on the sides of the cooling walls (5) in contact with the coke and are held in front of the pipes or the highly thermally conductive material (11) by means of fastening elements (13) guided through the webs (12). To achieve the taper according to the invention, the layer of highly thermally conductive material arranged between the tubes and the wear plates can have different thicknesses, ie. H. the thickness decreases from top to bottom.
- (1) Einfüllöffnung des Kokses(1) Coke fill opening
- (2) Außenwände der Kühlkammer(2) outer walls of the cooling chamber
- (3) Stützwände(3) retaining walls
- (4) Oberkante von (3) mit Verachleißschicht(4) top edge of (3) with wear layer
- (5) innere Rühlwände(5) internal bulkheads
- (6) Kokskühldchacht(6) Coke cooling shaft
- (7) Kühlmittelverteiler(7) Coolant distributor
- (8) Kühlrohre(8) cooling pipes
- (9) Sammler(9) collectors
- (10) Verachleißplatten(10) Wear plates
- (11) hochwärmeleitfähiges Material(11) highly thermally conductive material
- (12) Stege(12) webs
- (13) Befestigungsschrauben für (10)(13) fastening screws for (10)
- (14) Oberkante von (5)(14) top edge of (5)
- (15) VerschleiBkante(15) Wear edge
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86111408T ATE57952T1 (en) | 1985-08-30 | 1986-08-18 | COKE DRY COOLING CHAMBER. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3530984 | 1985-08-30 | ||
DE3530984A DE3530984C1 (en) | 1985-08-30 | 1985-08-30 | Coke dry cooling chamber |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0212611A2 true EP0212611A2 (en) | 1987-03-04 |
EP0212611A3 EP0212611A3 (en) | 1987-12-02 |
EP0212611B1 EP0212611B1 (en) | 1990-10-31 |
Family
ID=6279735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86111408A Expired - Lifetime EP0212611B1 (en) | 1985-08-30 | 1986-08-18 | Coke dry quenching chamber |
Country Status (4)
Country | Link |
---|---|
US (1) | US4832795A (en) |
EP (1) | EP0212611B1 (en) |
AT (1) | ATE57952T1 (en) |
DE (1) | DE3530984C1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5094292A (en) * | 1991-06-10 | 1992-03-10 | Buckshaw Dennis J | Tube shield |
US5795445A (en) * | 1996-07-10 | 1998-08-18 | Citgo Petroleum Corporation | Method of controlling the quench of coke in a coke drum |
US5827403A (en) * | 1996-07-10 | 1998-10-27 | Citgo Petroleum Corporation | Method of designing and manufacturing a delayed coker drum |
US6039844A (en) * | 1998-10-09 | 2000-03-21 | Citgo Petroleum Corporation | Containment system for coke drums |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1091080B (en) * | 1954-10-23 | 1960-10-20 | Steinmueller Gmbh L & C | Device for dry coke cooling |
BE674174A (en) * | 1965-02-01 | 1966-04-15 | ||
US4188915A (en) * | 1975-12-05 | 1980-02-19 | Dr. C. Otto & Comp. G.M.B.H. | Water-cooled, high-temperature gasifier |
EP0071804A2 (en) * | 1981-08-01 | 1983-02-16 | Thyssen Industrie Ag | Process and apparatus for cooling bulky material |
DE3338804A1 (en) * | 1983-10-26 | 1985-05-15 | M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München | Heat-exchange tubes |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US921878A (en) * | 1906-08-28 | 1909-05-18 | Power Specialty Company Of New York | Steam-superheater. |
DE3013722C2 (en) * | 1980-04-10 | 1984-07-05 | Carl Still Gmbh & Co Kg, 4350 Recklinghausen | Device for dry cooling of glowing coke |
-
1985
- 1985-08-30 DE DE3530984A patent/DE3530984C1/en not_active Expired
-
1986
- 1986-08-18 AT AT86111408T patent/ATE57952T1/en not_active IP Right Cessation
- 1986-08-18 EP EP86111408A patent/EP0212611B1/en not_active Expired - Lifetime
-
1987
- 1987-12-31 US US07/142,288 patent/US4832795A/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1091080B (en) * | 1954-10-23 | 1960-10-20 | Steinmueller Gmbh L & C | Device for dry coke cooling |
BE674174A (en) * | 1965-02-01 | 1966-04-15 | ||
US4188915A (en) * | 1975-12-05 | 1980-02-19 | Dr. C. Otto & Comp. G.M.B.H. | Water-cooled, high-temperature gasifier |
EP0071804A2 (en) * | 1981-08-01 | 1983-02-16 | Thyssen Industrie Ag | Process and apparatus for cooling bulky material |
DE3338804A1 (en) * | 1983-10-26 | 1985-05-15 | M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München | Heat-exchange tubes |
Non-Patent Citations (1)
Title |
---|
TECHNISCHE MITTEILUNGEN, 75. Jahrgang, Heft 9, September 1982, Seiten 434-439, DE; H. DUNGS: "Kokstrockenk}hlung mit K}hlw{nden im Koksschacht" * |
Also Published As
Publication number | Publication date |
---|---|
EP0212611A3 (en) | 1987-12-02 |
DE3530984C1 (en) | 1986-07-10 |
EP0212611B1 (en) | 1990-10-31 |
US4832795A (en) | 1989-05-23 |
ATE57952T1 (en) | 1990-11-15 |
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