EP1419221B1 - Method for scavenging precoolers of a coking plant - Google Patents
Method for scavenging precoolers of a coking plant Download PDFInfo
- Publication number
- EP1419221B1 EP1419221B1 EP02764842A EP02764842A EP1419221B1 EP 1419221 B1 EP1419221 B1 EP 1419221B1 EP 02764842 A EP02764842 A EP 02764842A EP 02764842 A EP02764842 A EP 02764842A EP 1419221 B1 EP1419221 B1 EP 1419221B1
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- European Patent Office
- Prior art keywords
- tar
- precoolers
- liquid phase
- naphthalene
- precooler
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004939 coking Methods 0.000 title claims abstract description 6
- 230000002000 scavenging effect Effects 0.000 title abstract 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 68
- 239000007787 solid Substances 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 239000007859 condensation product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 23
- 239000000571 coke Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000012717 electrostatic precipitator Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
- C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
-
- 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
- C10B43/00—Preventing or removing incrustations
- C10B43/02—Removing incrustations
- C10B43/08—Removing incrustations with liquids
-
- 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
- C10B43/00—Preventing or removing incrustations
- C10B43/14—Preventing incrustations
Definitions
- the invention relates to a method for flushing pre-cooling of a coking plant according to the preamble of claim 1.
- the Koksofenrohgas is first cooled in a direct raw gas cooling with the so-called template sprinkling water in a template.
- the Koksofenrohgas is cooled to a temperature of about 80 ° C and at the same time washed out part of the entrained solids content from the Koksofenrohgas and deposited in the liquid phase, together with the tar and condensate.
- the remaining solids content which is bound in the form of aerosols to the finest tar and water drops, passes with the Koksofenrohgas in the so-called precooler.
- the Koksofenrohgas is cooled in an indirect cooling of about 80 ° C to about 20 ° C. During this cooling, most of the naphthalene contained in the raw coke oven gas sublimes.
- tarry solids-containing ingredients of Koksofenrohgases are deposited on the outer walls of the cooling tubes of the precooler. In connection with the sublimated naphthalene there is the danger that it will come after a relatively short period of operation to blockages of the precooler.
- the precipitate deposited in the pre-coolers and the naphthalene-containing purge water can not be directly promoted to Teerscheidung with a temperature of about 20 ° C, otherwise there would be emulsion formation and the Teerscheidung would not work. Therefore, the pre-cooling condensates are usually pumped back to the individual Rohgasvorlagen the coke oven batteries with the naphthalene-containing rinse tar and mixed there with the hot auskondens faced from the coke oven condensed liquid phase.
- Non-prepublished DE 100 51 349 A1 discloses a process for recovering naphthalene from raw coke oven gas, in which the raw coke oven gas is cooled and the naphthalene contained in the coke oven raw gas is directly recovered.
- the non-prepublished DE 100 07 503 A1 discloses a process for the treatment of raw coke oven gas, in which the Koksofenrohgas is passed after cooling in the template by an electrostatic precipitator and then in the pre-cooler, wherein the flow of the electrostatic precipitator is used for rinsing.
- DE 26 52 499 A1 discloses a method for cooling the Koksofenrohgases, in which the precooler is divided into two stages, wherein in the first stage no precooling is carried out and in the second stage, a sprinkling of the gas with the circulated run the precooling condensate is made.
- DE 36 14 851 A1 discloses a method for flushing pre-coolers of a coking plant, in which the pre-coolers are rinsed with the liquid phase obtained from the original. In addition, it is proposed to feed into the Koksofenrohgas the lighter components (BTX aromatics) the Koksofenrohgas so that in the precooler a sufficient amount of solvent for the sublimated naphthalene is present in the precooler.
- the lighter components BTX aromatics
- the invention has for its object to provide a method available in which a blockage of the precooler is reliably avoided by Naphthalinablagerache and thus high availability of the precooler is guaranteed and in which also unnecessary additional cleaning process.
- the method according to the invention is based on the idea of using the liquid phase obtained in the direct raw gas cooling in the crude gas feed, which contains a relatively naphthalene tar, for rinsing the precoolers.
- the liquid phase of at least one crude gas feedstock is not mixed with the precooling condensates containing the rinse tar enriched with naphthalene and collected in a separate tar separator.
- This separately collected liquid phase contains the particularly naphthalene tar.
- the existing tar separator can be used. This has the advantage that no additional tar separator and thus additional investments are required.
- this naphtha-liquid phase is used for rinsing the radiator tubes in the pre-coolers.
- the water content of the separately collected liquid phase can be separated according to a development in the separate tar separator.
- the naphthalene tar can also be mixed with water for use as a rinse tar.
- the tar or the liquid phase can be freed from the solids in a tar centrifuge. This procedure ensures that no solids pass through the tar or the liquid phase into the precooler.
- the naphthalene of the crude coke oven gas sublimates on cooling from about 80 ° C to about 20 ° C and is deposited on the cooling tubes of the precooler from. It is now possible to prevent clogging of the precooler by continuously purging it with the liquid phase obtained from at least one raw gas receiver which is not charged with precooling condensates with the naphthalene tar.
- Rinsing with the naphthalene tar can in principle be carried out with all suitable nozzles, preferably in the upper region of the precooler. Since the tar is low in naphthalene, the task of tar in the precooler at only one point is sufficient for the success of the dishwashing process.
- the rinsing should take place in three levels, above, in the middle and below. This ensures in any case that deposits on the radiator pipes do not arise.
- the rinsing in the pre-cooler with a per se known baffle nozzle (DE-PS 197 48 693).
- the baffle ring nozzles ensure optimum distribution of the naphthalene tar on the tubes and the inner walls of the precoolers.
- the tarry and aqueous condensates running off at the bottom of the pre-coolers are conveyed, as usual, back to the still remaining raw gas templates, where they are processed together with the liquid phase obtained in the direct raw-gas cooling.
- a continuous pre-cooling operation can be maintained since deposits on the radiator tubes do not arise and the additional cleaning operations are no longer necessary. It also becomes the emissions that occur during the additional cleaning processes (cleaning with steam) avoided. Rinsing with naphthalene tar significantly increases the availability of pre-cooling. The investment costs are reduced because fewer precoolers must be provided. Since the cleaning processes can be omitted, also reduce the staff and material costs.
- Continuous pre-cooling operation ensures compliance with constant low coke oven raw gas temperatures at the pre-cooler outlet. It improves the coke oven gas quality, as the hydrogen sulfide, Anmioniak- and Benzolauswaschung can be made more effective at a constant low temperature. When benzene production no corrosion occur because the hydrogen sulphide and ammonia-containing condensates are avoided.
- the treatment of Koksofenrohgases is shown schematically.
- the Koksofenrohgas coming from the coke ovens 1 is cooled in templates 2 and 2a with the help of irrigation water 14 directly to about 80 ° C and passed into the precooler 3.
- the raw coke oven gas is conveyed into a coke oven gas purification 4 before it reaches a consumer 5.
- the effluent from the precoolers 3 condensates with the naphthalene-rich purge water are conveyed via a line 13 to the template 2, where there is a Erissennung and mixing with the costs incurred in the direct Rohgaslcühlung tar.
- This liquid phase from the receiver 2 is passed via a line 9 in a tar separator 6 for separating the tar from the carbon water. Via a line 7, the carbonic water is conveyed for further processing.
- the separated naphthalene-rich tar is transported via a line 8 for loading.
- the liquid phase from the receiver 2a is passed via a line 10 into a separate tar separator 11 and separated into carbon water and naphthalene tar.
- the naphthalene tar is conveyed via a line 12 to the precoolers 3 and used there for purging the cooling tubes.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Spülung von Vorkühlem einer Kokerei gemäß dem Oberbegriff des Anspruchs 1.The invention relates to a method for flushing pre-cooling of a coking plant according to the preamble of
Das bei der Verkokung von Steinkohle entstehende braungelbe Gemisch aus Gasen und Dämpfen, das sogenannte Koksofenrohgas, beinhaltet einen nicht unerheblichen Feststoff- und Naphthalinanteil. Das Koksofenrohgas wird zunächst in einer direkten Rohgaskühlung mit dem sogenannten Vorlagenberieselungswasser in einer Vorlage gekühlt. Dabei wird das Koksofenrohgas auf eine Temperatur von ca. 80°C gekühlt und gleichzeitig ein Teil des mitgeführten Feststoffanteils aus dem Koksofenrohgas ausgewaschen und in der flüssigen Phase mitsamt dem Teer und Kondensat abgeschieden.The brownish-yellow mixture of gases and vapors produced during the coking of hard coal, the so-called coke oven raw gas, contains a not inconsiderable amount of solids and naphthalene. The Koksofenrohgas is first cooled in a direct raw gas cooling with the so-called template sprinkling water in a template. The Koksofenrohgas is cooled to a temperature of about 80 ° C and at the same time washed out part of the entrained solids content from the Koksofenrohgas and deposited in the liquid phase, together with the tar and condensate.
Der restliche Feststoffanteil, der in Form von Aerosolen an feinste Teer- und Wassertropfen gebunden ist, gelangt mit dem Koksofenrohgas in die sogenannten Vorkühler. Dort wird das Koksofenrohgas in einer indirekten Kühlung von ca. 80°C auf ca. 20°C gekühlt. Bei dieser Abkühlung sublimiert ein Großteil des in dem Koksofenrohgas enthaltenen Naphthalins. Gleichzeitig werden teerige, feststoffhaltige Inhaltsstoffe des Koksofenrohgases auf den Außenwänden der Kühlrohre der Vorkühler abgeschieden. In Verbindung mit dem sublimierten Naphthalin besteht die Gefahr, dass es nach relativ kurzer Betriebszeit zu Verstopfungen des Vorkühlers kommt. Durch eine permanente Berieselung mit der aus der Vorlage gewonnenen Flüssigphase (Teer-Wasseremulsion - ca. 30 % Teer und ca. 70% Wasser) im oberen und mittleren Teil der Vorkühler sollen die Feststoff- und Naphthalinablagerungen auf den Kühlrohren gelöst werden. Da diese Teer-Wasseremulsion bereits nahezu mit Naphthalin gesättigt ist und außerdem Feststoffe beinhaltet, führt diese permanente Vorkühlerberieselung zu keiner wesentlichen Verfügbarkeitserhöhung bei der Koksofenrohgaskühlung. Aus diesem Grunde ist es üblich, dass die Vorkühler im ständigen Rhythmus, teilweise täglich, mittels Dampf gereinigt werden müssen. Da diese Vorkühler während des Reinigungsvorganges nicht zur Verfügung stehen, müssen zusätzliche Vorkühlerkapazitäten ständig betriebsbereit sein.The remaining solids content, which is bound in the form of aerosols to the finest tar and water drops, passes with the Koksofenrohgas in the so-called precooler. There, the Koksofenrohgas is cooled in an indirect cooling of about 80 ° C to about 20 ° C. During this cooling, most of the naphthalene contained in the raw coke oven gas sublimes. At the same time tarry, solids-containing ingredients of Koksofenrohgases are deposited on the outer walls of the cooling tubes of the precooler. In connection with the sublimated naphthalene there is the danger that it will come after a relatively short period of operation to blockages of the precooler. Through a permanent Sprinkling with the liquid phase obtained from the template (tar water emulsion - about 30% tar and about 70% water) in the upper and middle part of the precooler, the solid and Naphthalinablagerungen to be solved on the cooling tubes. Since this tar water emulsion is already nearly saturated with naphthalene and also contains solids, this permanent precooler slurry does not result in a substantial increase in availability of coke oven crude gas cooling. For this reason, it is common that the precooler in constant rhythm, some daily, need to be cleaned by steam. Since these precoolers are not available during the cleaning process, additional precooling capacities must be constantly ready for operation.
Das in den Vorkühlern abgeschiedene Kondensat sowie der naphthalinhaltige Spülteer kann mit einer Temperatur von ca. 20°C nicht direkt zur Teerscheidung gefördert werden, da es dort sonst zur Emulsionsbildung kommt und die Teerscheidung nicht mehr funktionieren würde. Daher werden die Vorkühlerkondensate mit dem naphthalinhaltigen Spülteer üblicherweise zu den einzelnen Rohgasvorlagen der Koksofenbatterien zurückgepumpt und dort mit der heißen, aus dem Koksofen kommenden auskondensierten Flüssigphase vermischt. Dabei wird allerdings nicht nur die Temperatur des zurückgeführten Vorkühlerkondensates einschließlich des Spülteers auf ca. 80°C angehoben, sondern es findet gleichzeitig eine Vermischung mit dem aus dem Koksofen kommenden Teer statt, so dass letztlich nur ein mit Naphthalin angereicherter Teer zur Teerscheidung gelangt und zur Spülung der Vorkühler zur Verfügung steht.The precipitate deposited in the pre-coolers and the naphthalene-containing purge water can not be directly promoted to Teerscheidung with a temperature of about 20 ° C, otherwise there would be emulsion formation and the Teerscheidung would not work. Therefore, the pre-cooling condensates are usually pumped back to the individual Rohgasvorlagen the coke oven batteries with the naphthalene-containing rinse tar and mixed there with the hot auskondensierten from the coke oven condensed liquid phase. In this case, however, not only the temperature of the recirculated precooler condensate including the purge water is raised to about 80 ° C, but it takes place at the same time mixing with the coming out of the coke oven tar, so that ultimately only one enriched with naphthalene tar for tea separation arrives and Flushing the precooler is available.
Um die geforderten Grenzwerte für den Schwefelwasserstoff- und den Ammoniakgehalt im gereinigten Koksofengas nach der Gaswäsche zu erreichen, ist die konstante Einhaltung von niedrigen Vorkühleraustrittstemperaturen erforderlich. Es muss eine zuverlässige Vorkühlung des Koksofenrohgases kontinuierlich gewährleistet sein und eine Verstopfung der Vorkühler verhindert werden.In order to achieve the required limits for the hydrogen sulfide and ammonia content in the purified coke oven gas after gas scrubbing, the constant maintenance of low precooler outlet temperatures is required. A reliable pre-cooling of the Koksofenrohgases must be continuously ensured and a blockage of the pre-cooler can be prevented.
Die nicht vorveröffentlichte DE 100 51 349 A1 offenbart ein Verfahren zur Gewinnung von Naphthalin aus Koksofenrohgas, bei dem das Koksofenrohgas gekühlt und das in dem Koksofenrohgas enthaltene Naphthalin direkt gewonnen wird.Non-prepublished DE 100 51 349 A1 discloses a process for recovering naphthalene from raw coke oven gas, in which the raw coke oven gas is cooled and the naphthalene contained in the coke oven raw gas is directly recovered.
Die nicht vorveröffentlichte DE 100 07 503 A1 offenbart ein Verfahren zur Behandlung von Koksofenrohgas, bei dem das Koksofenrohgas nach Kühlung in der Vorlage durch einen Elektrofilter und anschließend in die Vorkühler geführt wird, wobei der Ablauf des Elektrofilters zum Spülen in den Vorkühlem verwendet wird.The non-prepublished DE 100 07 503 A1 discloses a process for the treatment of raw coke oven gas, in which the Koksofenrohgas is passed after cooling in the template by an electrostatic precipitator and then in the pre-cooler, wherein the flow of the electrostatic precipitator is used for rinsing.
Aus der DE 34 23 798 C2 ist es bekannt, dass das Koksofenrohgas nach Kühlung in der Vorlage zunächst durch einen Elektrofilter und anschließend in die Vorkühler geführt wird. Durch das Elektrofilter werden zwar ein Großteil der Feststoffe in dem Koksofenrohgas abgeschieden, die Gefahr von Naphthalinablagerungen auf den Kühlrohren der Vorkühler wird jedoch nicht beseitigt. Auch bei dieser Verfahrensweise muss eine Berieselung mit einem Teer-Wasser-Gemisch zur Ablösung der Ablagerungen vorgenommen werden.From DE 34 23 798 C2 it is known that the Koksofenrohgas is first performed by cooling in the template by an electrostatic precipitator and then in the precooler. Although the electrostatic precipitator, a majority of the solids are deposited in the Koksofenrohgas, the risk of Naphthalinablagerungen on the cooling tubes of the precooler is not eliminated. Even with this procedure, a sprinkling with a tar-water mixture must be made to replace the deposits.
In der DE 26 52 499 A1 wird ein Verfahren zur Kühlung des Koksofenrohgases offenbart, bei dem der Vorkühler in zwei Stufen unterteilt ist, wobei in der ersten Stufe keine Vorkühlerspülung vorgenommen wird und in der zweiten Stufe eine Berieselung des Gases mit dem im Kreislauf geführten Ablauf des Vorkühlerkondensates vorgenommen wird.In DE 26 52 499 A1 discloses a method for cooling the Koksofenrohgases is disclosed, in which the precooler is divided into two stages, wherein in the first stage no precooling is carried out and in the second stage, a sprinkling of the gas with the circulated run the precooling condensate is made.
Die DE 36 14 851 A1 offenbart ein Verfahren zur Spülung von Vorkühlern einer Kokerei, bei dem die Vorkühler mit der aus der Vorlage gewonnenen Flüssigphase gespült werden. Zusätzlich wird vorgeschlagen, in das Koksofenrohgas die leichteren Komponenten (BTX-Aromaten) dem Koksofenrohgas zuzuführen, damit in dem Vorkühler eine ausreichende Lösungsmittelmenge für das sublimierte Naphthalin im Vorkühler vorhanden ist.DE 36 14 851 A1 discloses a method for flushing pre-coolers of a coking plant, in which the pre-coolers are rinsed with the liquid phase obtained from the original. In addition, it is proposed to feed into the Koksofenrohgas the lighter components (BTX aromatics) the Koksofenrohgas so that in the precooler a sufficient amount of solvent for the sublimated naphthalene is present in the precooler.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Verfügung zu stellen, bei dem eine Verstopfung der Vorkühler durch Naphthalinablagerungen zuverlässig vermieden wird und somit eine hohe Verfügbarkeit der Vorkühler gewährleistet ist und bei dem sich außerdem zusätzliche Reinigungsverfahren erübrigen.The invention has for its object to provide a method available in which a blockage of the precooler is reliably avoided by Naphthalinablagerungen and thus high availability of the precooler is guaranteed and in which also unnecessary additional cleaning process.
Diese Aufgabe wird durch die Merkmale des Patentanspruchs 1 gelöst.This object is solved by the features of
Weiterbildungen erfolgen gemäß den Merkmalen der Unteransprüche.Further developments take place according to the features of the subclaims.
Das erfindungsgemäße Verfahren beruht auf dem Grundgedanken, die bei der direkten Rohgaskühlung in der Rohgasvorlage anfallende Flüssigphase, die einen relativ naphthalinarmen Teer enthält, zur Spülung der Vorkühler zu verwenden.The method according to the invention is based on the idea of using the liquid phase obtained in the direct raw gas cooling in the crude gas feed, which contains a relatively naphthalene tar, for rinsing the precoolers.
Durch Versuche wurde herausgefunden, dass der in der Vorlage durch direkte Kühlung auf eine Temperatur von ca. 80°C abgeschiedene Teer nur einen geringen Anteil (ca. 2 %) an Naphthalin enthält. Dieses Ergebnis war überraschend, da bisher davon ausgegangen wurde, dass aufgrund der guten Löslichkeit des Naphthalins im Teer ein großer Anteil des im Koksofenrohgas enthaltenen Naphthalins mit dem Teer abgeschieden würde. Tatsächlich erfolgt die Anreicherung des Teers in der Vorlage mit Naphthalin durch die oben beschriebene Rückführung der Vorkühlerkondensate.It has been found by experiments that the tar deposited in the original by direct cooling to a temperature of about 80 ° C. contains only a small proportion (about 2%) of naphthalene. This result was surprising, since it was previously assumed that due to the good solubility of naphthalene in the tar, a large proportion of the naphthalene contained in Koksofenrohgas would be deposited with the tar. In fact, the enrichment of the tar in the feed with naphthalene is accomplished by the recirculation of the precooling condensates described above.
Demzufolge wird erfindungsgemäß die Flüssigphase mindestens einer Rohgasvorlage nicht mit den Vorkühlerkondensaten, die den bereits mit Naphthalin angereicherten Spülteer enthalten, vermischt und in einem separaten Teerscheider gesammelt. Diese separat gesammelte Flüssigphase enthält den besonders naphthalinarmen Teer. Als separater Teerscheider kann der vorhandene Teerscheider verwendet werden. Das hat den Vorteil, dass kein zusätzlicher Teerscheider und damit zusätzliche Investitionen erforderlich sind. Erfindungsgemäß wird diese naphtltalinarme Flüssigphase zur Spülung der Kühlerrohre in den Vorkühlem verwendet.Accordingly, according to the invention, the liquid phase of at least one crude gas feedstock is not mixed with the precooling condensates containing the rinse tar enriched with naphthalene and collected in a separate tar separator. This separately collected liquid phase contains the particularly naphthalene tar. As a separate tar separator the existing tar separator can be used. This has the advantage that no additional tar separator and thus additional investments are required. According to the invention, this naphtha-liquid phase is used for rinsing the radiator tubes in the pre-coolers.
Der Wasseranteil der gesondert gesammelten Flüssigphase kann gemäß einer Weiterbildung in dem separaten Teerscheider abgeschieden werden. Der naphthalinarme Teer kann für die Verwendung als Spülteer auch mit Wasser gemischt sein.The water content of the separately collected liquid phase can be separated according to a development in the separate tar separator. The naphthalene tar can also be mixed with water for use as a rinse tar.
Gemäß einer weiteren Ausgestaltung kann der Teer oder die Flüssigphase in einer Teerzentrifuge von den Feststoffen befreit werden. Bei dieser Verfahrensweise ist sichergestellt, dass keine Feststoffe durch den Teer bzw. die Flüssigphase in die Vorlcühler gelangen.According to a further embodiment, the tar or the liquid phase can be freed from the solids in a tar centrifuge. This procedure ensures that no solids pass through the tar or the liquid phase into the precooler.
Wie bereits dargestellt, sublimiert das Naphthalin des Koksofenrohgases bei der Abkühlung von ca. 80°C auf ca. 20°C und lagert sich auf den Kühlrohren der Vorkühler ab. Es gelingt nun, ein Verstopfen der Vorkühler dadurch zu verhindern, dass diese kontinuierlich mit dem zuvor aus mindestens einer Rohgasvorlage, die nicht mit Vorkühlerkondensaten beaufschlagt wird, gewonnenen Flüssigphase mit dem naphthalinarmen Teer gespült werden.As already mentioned, the naphthalene of the crude coke oven gas sublimates on cooling from about 80 ° C to about 20 ° C and is deposited on the cooling tubes of the precooler from. It is now possible to prevent clogging of the precooler by continuously purging it with the liquid phase obtained from at least one raw gas receiver which is not charged with precooling condensates with the naphthalene tar.
Das Spülen mit dem naphthalinarmen Teer kann grundsätzlich mit allen dafür geeigneten Düsen, vorzugsweise im oberen Bereich des Vorkühlers, durchgeführt werden. Da der Teer naphthalinarm ist, ist die Aufgabe des Teers in den Vorkühler an nur einer Stelle für den Spülerfolg ausreichend.Rinsing with the naphthalene tar can in principle be carried out with all suitable nozzles, preferably in the upper region of the precooler. Since the tar is low in naphthalene, the task of tar in the precooler at only one point is sufficient for the success of the dishwashing process.
Gemäß einer weiteren Ausgestaltung der Erfindung sollte das Spülen in drei Ebenen, oben, in der Mitte und unten erfolgen. Dadurch ist auf jeden Fall sichergestellt, dass Ablagerungen an den Kühlerrohren nicht entstehen.According to a further embodiment of the invention, the rinsing should take place in three levels, above, in the middle and below. This ensures in any case that deposits on the radiator pipes do not arise.
Bevorzugt ist das Spülen in den Vorkühlem mit einer an sich bekannten Prallringdüse (DE-PS 197 48 693). Die Prallringdüsen sorgen für eine optimale Verteilung des naphthalinarmen Teeres auf den Rohren und den Innenwandungen der Vorkühler. Die am Fuß der Vorkühler ablaufenden teerigen und wässrigen Kondensate werden wie üblich wieder zu den noch verbleibenden Rohgasvorlagen gefördert, wo sie gemeinsam mit der bei der direkten Rohgaskühlung anfallenden flüssigen Phase verarbeitet werden.Preferably, the rinsing in the pre-cooler with a per se known baffle nozzle (DE-PS 197 48 693). The baffle ring nozzles ensure optimum distribution of the naphthalene tar on the tubes and the inner walls of the precoolers. The tarry and aqueous condensates running off at the bottom of the pre-coolers are conveyed, as usual, back to the still remaining raw gas templates, where they are processed together with the liquid phase obtained in the direct raw-gas cooling.
Durch das erfindungsgemäße Verfahren kann ein kontinuierlicher Vorkühlerbetrieb aufrechterhalten werden, da Ablagerungen an den Kühlerrohren nicht entstehen und die zusätzlichen Reinigungsvorgänge nicht mehr erforderlich sind. Es werden außerdem die bei den zusätzlichen Reinigungsprozessen (Reinigung mit Dampf) auftretenden Emissionen vermieden. Durch die Spülung mit dem naphthalinarmen Teer wird die Verfügbarkeit der Vorkühlung deutlich erhöht. Die Investitionskosten reduzieren sich, da weniger Vorkühler vorgesehen werden müssen. Da die Reinigungsvorgänge wegfallen können, reduzieren sich ebenfalls die Personal- und Materialkosten.By means of the method according to the invention, a continuous pre-cooling operation can be maintained since deposits on the radiator tubes do not arise and the additional cleaning operations are no longer necessary. It also becomes the emissions that occur during the additional cleaning processes (cleaning with steam) avoided. Rinsing with naphthalene tar significantly increases the availability of pre-cooling. The investment costs are reduced because fewer precoolers must be provided. Since the cleaning processes can be omitted, also reduce the staff and material costs.
Durch den kontinuierlichen Vorkühlerbetrieb ist die Einhaltung von konstanten niedrigen Koksofenrohgastemperaturen am Vorkühleraustritt gewährleistet. Es verbessert sich die Koksofengasqualität, da die Schwefelwasserstoff , Anmioniak- und Benzolauswaschung bei konstant niedriger Temperatur effektiver vorgenommen werden kann. Bei der Benzolgewinnung treten keine Korrosionen auf, da die schwefelwasserstoff- und ammoniakhaltigen Kondensate vermieden werden.Continuous pre-cooling operation ensures compliance with constant low coke oven raw gas temperatures at the pre-cooler outlet. It improves the coke oven gas quality, as the hydrogen sulfide, Anmioniak- and Benzolauswaschung can be made more effective at a constant low temperature. When benzene production no corrosion occur because the hydrogen sulphide and ammonia-containing condensates are avoided.
Die vorgenannten, sowie die beanspruchten und im Ausführungsbeispiel beschriebenen, erfindungsgemäß zu verwendenden Verfahrensschritte unterliegen hinsichtlich ihrer Verfahrensbedingungen keinen besonderen Ausnahmebedingungen, so dass die in dem jeweiligen Anwendungsgebiet bekannten Auswahlkriterien im Rahmen der Ansprüche uneingeschränkt Anwendung finden können.The above-mentioned, as well as the claimed and described in the exemplary embodiment, to be used according to the invention process steps are not subject to any special conditions of exception with respect to their process conditions, so that the selection criteria known in the respective field of application can be fully applied within the scope of the claims.
Weitere Einzelheiten, Merkmale und Vorteile des Gegenstandes der Erfindung ergeben sich aus der nachfolgenden Beschreibung der zugehörigen Zeichnung, in der beispielhaft eine bevorzugte Ausführungsform eines Verfahrens zur Kühlung von Koksofenrohgas dargestellt ist. In der Zeichnung zeigt
Figur 1- ein Verfahrensschema des Verfahrens zur Spülung der Vorkühler mit dem naphthalinarmen Teer.
- FIG. 1
- a process scheme of the process for purifying the precooler with the naphthalene tar.
In der Figur 1 ist die Behandlung des Koksofenrohgases schematisch dargestellt. Das aus den Koksöfen 1 kommende Koksofenrohgas wird in Vorlagen 2 und 2a mit Hilfe von Berieselungswasser 14 direkt auf ca. 80°C gekühlt und in die Vorkühler 3 geleitet. Von den Vorkühlern 3 wird das Koksofenrohgas in eine Koksofengasreinigung 4 gefördert, bevor es zu einem Verbraucher 5 gelangt.In the figure 1, the treatment of Koksofenrohgases is shown schematically. The Koksofenrohgas coming from the
Die aus den Vorkühlern 3 ablaufenden Kondensate mit dem naphthalinreichen Spülteer werden über eine Leitung 13 zur Vorlage 2 gefördert , wo eine Erwännung und Vermischung mit dem bei der direkten Rohgaslcühlung anfallenden Teer stattfindet. Diese Flüssigphase aus der Vorlage 2 wird über eine Leitung 9 in einen Teerscheider 6 zur Trennung des Teers von dem Kohlewasser geführt. Über eine Leitung 7 wird das Kohlewasser zur weiteren Aufarbeitung gefördert. Der abgeschiedene naphthalinreiche Teer wird über eine Leitung 8 zur Verladung transportiert. Die Flüssigphase aus der Vorlage 2a wird über eine Leitung 10 in einen separaten Teerscheider 11 geleitet und in Kohlewasser und naphthalinarmen Teer getrennt. Der naphthalinarme Teer wird über eine Leitung 12 zu den Vorkühlern 3 gefördert und dort zum Spülen der Kühlrohre verwendet.The effluent from the
- 11
- Koksofencoke oven
- 22
- Vorlagetemplate
- 2a2a
- Vorlagetemplate
- 33
- Vorkühlerprecooler
- 44
- KoksofengasreinigungKoksofengasreinigung
- 55
- Verbraucherconsumer
- 66
- TeerscheiderTeerscheider
- 77
- Leitung (Kohlewasser)Pipe (coal water)
- 88th
- Leitung (Teer)Pipe (tar)
- 99
- Leitung (Flüssigphase mit naphthalinreichem Teer)Line (liquid phase with naphthalene-rich tar)
- 1010
- Leitung (Flüssigphase mit naphthalinarmem Teer)Conduction (liquid phase with low naphthalene tar)
- 1111
- separater Teerscheiderseparate tar separator
- 1212
- Leitung (naphthalinarmer Spülteer)Line (naphthalinarmer Spülteer)
- 1313
- Leitung (Vorkühlerkondensate mit naphthalinreichem Teer)Line (precooling condensates with naphthalene-rich tar)
- 1414
- Berieselungswassersprinkler water
Claims (6)
- A method for flushing precoolers of a coking plant, in which the precoolers are flushed with the liquid phase obtained from the collecting main, characterised in that a liquid phase is used to flush the precoolers, which liquid phase originates from at least one collecting main which is not acted upon with precooler condensates.
- A method according to Claim 1, characterised in that the liquid phase is conducted from at least one collecting main, which is not acted upon with precooler condensates, into a separate tar separator, and the tar poor in naphthalene obtained in the tar separator is used in the precoolers for flushing.
- A method according to Claim 1 and 2, characterised in that the tar poor in naphthalene obtained in the separate tar separator or the liquid phase is conducted into a tar centrifuge to separate out the solids and is then used in the precoolers for flushing.
- A method according to Claim 1 to 3, characterised in that the flushing takes place in the precoolers by means of impact ring nozzles.
- A method according to Claim 1 to 4, characterised in that the flushing takes place in the precoolers at a single feed location.
- A method according to Claim 1 to 5, characterised in that the flushing is carried out in the precoolers at the top, in the middle and at the bottom.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10139172 | 2001-08-15 | ||
| DE10139172A DE10139172C1 (en) | 2001-08-15 | 2001-08-15 | Rinsing pre-coolers of coking plant involves using liquid phase produced from collecting main which has not been impinged with pre-cooler condensate |
| PCT/EP2002/008978 WO2003016437A2 (en) | 2001-08-15 | 2002-08-10 | Method for scavenging precoolers of a coking plant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1419221A2 EP1419221A2 (en) | 2004-05-19 |
| EP1419221B1 true EP1419221B1 (en) | 2006-06-07 |
Family
ID=7694927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02764842A Expired - Lifetime EP1419221B1 (en) | 2001-08-15 | 2002-08-10 | Method for scavenging precoolers of a coking plant |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1419221B1 (en) |
| KR (1) | KR20040025935A (en) |
| CN (1) | CN1543497A (en) |
| AT (1) | ATE328985T1 (en) |
| AU (1) | AU2002329241A1 (en) |
| DE (2) | DE10139172C1 (en) |
| TW (1) | TW555844B (en) |
| WO (1) | WO2003016437A2 (en) |
| ZA (1) | ZA200400726B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413778A (en) * | 2017-04-27 | 2017-12-01 | 唐山钢铁集团有限责任公司 | A kind of cleaning method for reducing coking end cooler resistance |
| CN107916144B (en) * | 2017-12-21 | 2023-06-16 | 中冶焦耐(大连)工程技术有限公司 | Primary cooler spraying device with backwashing function and application method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614851A1 (en) * | 1986-05-02 | 1987-11-05 | Still Carl Gmbh Co Kg | METHOD FOR COOLING RAW GAS |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1074815B (en) * | 1960-02-04 | Fa Carl Still Recklinghausen | Process for obtaining carbon materials from coke oven gases | |
| DE2652499A1 (en) * | 1976-11-18 | 1978-05-24 | Otto & Co Gmbh Dr C | Cooling of coke oven gas - in two stages sepd. by spraying with condensate to remove naphthalene |
| DE3423798A1 (en) * | 1984-06-28 | 1986-01-09 | Bergwerksverband Gmbh, 4300 Essen | METHOD FOR SEPARATING THE WATER RESULTING FROM THE COCING PROCESS INTO A SMALL SALT-HIGH AND A LARGE SALT-LOW FRACTION |
| DE4012141A1 (en) * | 1990-04-14 | 1991-10-17 | Still Otto Gmbh | METHOD FOR PRE-COOKING RAW COOKING GAS AND FOR DESORPING WASHING WATER AND CONDENSATE OF COOKING |
| DE10007503B4 (en) * | 2000-02-18 | 2004-05-27 | Deutsche Montan Technologie Gmbh | Process for the treatment of raw coke oven gas |
| DE10051349B4 (en) * | 2000-10-17 | 2005-02-03 | Deutsche Montan Technologie Gmbh | Process and apparatus for recovering naphthalene from raw coke oven gas |
-
2001
- 2001-08-15 DE DE10139172A patent/DE10139172C1/en not_active Expired - Fee Related
-
2002
- 2002-07-24 TW TW091116448A patent/TW555844B/en not_active IP Right Cessation
- 2002-08-10 AT AT02764842T patent/ATE328985T1/en active
- 2002-08-10 EP EP02764842A patent/EP1419221B1/en not_active Expired - Lifetime
- 2002-08-10 CN CNA028160657A patent/CN1543497A/en active Pending
- 2002-08-10 WO PCT/EP2002/008978 patent/WO2003016437A2/en active IP Right Grant
- 2002-08-10 KR KR10-2004-7001543A patent/KR20040025935A/en not_active Application Discontinuation
- 2002-08-10 AU AU2002329241A patent/AU2002329241A1/en not_active Abandoned
- 2002-08-10 DE DE50207122T patent/DE50207122D1/en not_active Expired - Lifetime
-
2004
- 2004-01-29 ZA ZA200400726A patent/ZA200400726B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614851A1 (en) * | 1986-05-02 | 1987-11-05 | Still Carl Gmbh Co Kg | METHOD FOR COOLING RAW GAS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1543497A (en) | 2004-11-03 |
| AU2002329241A1 (en) | 2003-03-03 |
| EP1419221A2 (en) | 2004-05-19 |
| WO2003016437A3 (en) | 2003-09-25 |
| DE50207122D1 (en) | 2006-07-20 |
| ATE328985T1 (en) | 2006-06-15 |
| WO2003016437A2 (en) | 2003-02-27 |
| ZA200400726B (en) | 2004-03-02 |
| DE10139172C1 (en) | 2003-02-06 |
| KR20040025935A (en) | 2004-03-26 |
| TW555844B (en) | 2003-10-01 |
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