EP0245814B1 - Einrichtung zur Kühlung und zur Eliminierung von Feuchtigkeit, Naphtha und Tar von Kohlendestillationsgasen - Google Patents

Einrichtung zur Kühlung und zur Eliminierung von Feuchtigkeit, Naphtha und Tar von Kohlendestillationsgasen Download PDF

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Publication number
EP0245814B1
EP0245814B1 EP87106786A EP87106786A EP0245814B1 EP 0245814 B1 EP0245814 B1 EP 0245814B1 EP 87106786 A EP87106786 A EP 87106786A EP 87106786 A EP87106786 A EP 87106786A EP 0245814 B1 EP0245814 B1 EP 0245814B1
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Prior art keywords
tar
naphthalene
water
gas
temperature
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EP87106786A
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English (en)
French (fr)
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EP0245814A1 (de
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Emanuele Proface
Nicola Pascale
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Italimpianti SpA
Ilva SpA
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Italimpianti SpA
Ilva SpA
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Priority to AT87106786T priority Critical patent/ATE49992T1/de
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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

Definitions

  • the gas which is produced in coal-distilling plants contains - when flowing out of the distilling banks - steam, tar, naphthalene, anthracene oils, ammonia, raw benzol, hydrogen sulphide, and traces of other chemicals.
  • gas flowing out of the distilling banks is passed through a succession of apparatuses designed to remove both recoverable and undesired substances from said gas.
  • Gas, water, tar and anthracene oils flow together out of said header and are conveyed through a suitable piping to a separator to separate said gas therefrom.
  • Water, tar and anthracene oils, after separation from said gas, are conveyed to a decanter where said tar and anthracene oils will settle down onto the bottom to be then removed, and water is re-cycled.
  • the gas passing beyond said separator still contains all the by-products mentioned above, including the fractions of tar, anthracene oils and naphthalene that have not condensed during said cooling step.
  • the gas is purified by removal of the remaining tar and naphthalene therefrom.
  • this fraction of naphthalene is removed together with all the remaining tar.
  • said gas is scrubbed in water-cooling towers, where it is cooled to a temperature of 25 to 35°C, thus obtaining the complete condensation of tar and of a fraction of naphthalene that has been dissolved in said tar.
  • Tar is then separated from the water in a suitable decanter.
  • the remaining naphthalene is then removed from the gas in a scrubbing plant by means of suitable solvents, usually anthracene oils or automotive diesel oil. If anthracene oils are used, an oil-regenerating system is required, since said oils are quite expensive.
  • diesel oil requires no regenerating system, since it may be used as a fuel because the naphthalene therein causes no combustion trouble.
  • the use of diesel oil as a fuel involves an increase of costs in the combustion systems, because it is substituted for the less expensive coke-oven gas.
  • the process of the present invention in addition to the cooling and de-humidification of said gas, and to the complete removal of tar therefrom, enables the elimination of naphthalene from said gas with no need of solvents, such as oils or diesel oil, with resulting economy due to the lower capital and running costs - in that no regeneration of said oils is required and diesel oil need not be substituted for the less expensive coke-oven gas - and to the lower maintenance costs.
  • solvents such as oils or diesel oil
  • the gas flowing out of said header and having a temperature of 80-85 ° C is scrubbed and cooled by means of atomized water in a cooler wherein the scrubbing water has a temperature slightly above 0 ° C, usually about 10 ° C.
  • the gas flowing out of the top of the cooler may still contain residual droplets of water, particles of tar and naphthalene either incorporated or not in said droplets of water and to be removed in a successive cyclone separator or any other suitable separator, such as electrostatic filters, Venturi tubes, etc.
  • said gas Upon exiting from these devices, said gas is thoroughly devoid of tar and only contains the amount of gaseous naphthalene to saturate said gas at its post-cooling temperature. Thereafter, said gas is passed through the successive purifying and processing systems, just like in the conventional plants.
  • the scrubbing water flowing out of the cooling system contains a much higher rate of naphthalene than the water flowing out of the known plants, due to the lower cooling temperature, which has caused a much higher condensation of naphthalene.
  • naphthalene is absorbed by tar during the intimate contact therebetween and due to the solubility of naphthalene in tar and to the small amount which is found dissolved in the latter, usually about 5%.
  • the amount of naphthalene to be eliminated is much higher due to the lower cooling temperatures of gas; therefore, special and new provisions have been used therein to enhance the contact between tar and naphthalene, whereby the latter may be absorbed thouroughly by dissolution in the tar.
  • the scrubbing water exiting from the cooler is conveyed into a flotation and decantation tank, where the materials lighter than water - such as naphthalene flakes and foams, light oils, etc. - will float, and the heavier materials - such as tar, anthracene oils, etc. - will settle down.
  • materials lighter than water - such as naphthalene flakes and foams, light oils, etc. - will float, and the heavier materials - such as tar, anthracene oils, etc. - will settle down.
  • the floating materials including naphthalene are removed by suction from the surface of the scrubbing water in the tank, and the settled materials, mostly tar, are sucked from the bottom. Both of them, once sucked away, together with some of the water, are conveyed into a single piping where they are mixed into intimate contact with each other, which is enhanced by the turbulence caused by the pumping devices and the speed of the fluid, which is purposely maintained at suitable values.
  • the tar will absorb the naphthalene during the travel thereof through said piping, the latter having such a length whereby almost all the free naphthalene will be absorbed at the outlet thereof.
  • Said piping then discharges water and tar, that has absorbed most of the naphthalene, into the decanter which also receives the water deprived of gas in the separator following said header, the absorption of the still free residual naphthalene by the tar being continued in said decanter.
  • the tar is then allowed to settle down in said decanter and is discharged, while the water, now devoid of tar and naphthalene, is re-cycled.
  • Such water contains small particles of naphthalene which have not yet reached the surface owing to their small buoyancy resulting from their very small dimensions.
  • Such water is conveyed to said header and introduced at the bottom thereof, where it mixes with the water being sprayed for the first cooling of the gas and with the water that condenses therein, which is rich of tar having a low content of naphthalene because the latter, due to the high temperature therein, has only condensed to a minimum extent. Therefore, naphthalene will be dissolved easily and completely in the tar it contacts within said header and successively within the following piping, within the separator and finally in the tar decanter.
  • the degree of purification of gas from naphthalene depends upon the average temperature of said gas in the piping of the distribution network, because said temperature controls its condensation to the dew point thereof, with attendant fouling and clogging problems. In the countries where the ambient temperature is higher, higher percentages of naphthalene in the gas may be tolerated than in colder countries. This affects the selection of the various cooling temperatures for the gas, and of all the parameters affecting the greater or smaller extent of contact between tar and naphthalene such as to avoid any condensation within the gas distribution piping. These parameters may be varied in the same plant, from time to time, depending on the ambient temperatures, thus saving energy when the ambient temperature permits a higher concentration of naphthalene in the gas.
  • the naphthalene that has been removed from the gas is incorporated in the tar, and the latter may be used with no purification, for example, as a fuel. Should a purification of the tar be required for other utilizations, no additional costs are involved with respect to the known plants, because the tar produced in the latter also contains a percentage of naphthalene, usually about 5% as stated above, and the higher concentration thereof in the tar produced in the plant of the invention requires no particular plants and processes.
  • the recovery of naphthalene has a lower cost than with the purification systems heretofore known, because the entire recovery would be effected by distillation of only the tar.
  • the gas flows out of the banks of coke-ovens, only one of which is shown in the drawing for simplicity's sake and is indicated at 1, and is conveyed to the header 3 through the piping 2.
  • suitable water sprays will lower the temperature of the gas to 80-85 ° C. Due to this cooling action, the excess steam in the gas flowing out of said bank is condensed and will collect into the bottom 4 of the header 3 together with the water that has been used for cooling purposes.
  • Water, tar and gas will be conveyed into a piping 5 to reach a water-gas separator 6 where the gas is separated from the tar-containing water.
  • the gas pursues its travel in the piping 7, and water and tar are conveyed through the piping 8 into a decanter 9, where the tar will settle down onto the bottom due to its greater specific gravity with respect to water.
  • the tar on the bottom of the decanter is discharged through a piping 10 and is recovered.
  • first set of spray nozzles 13 for atomizing water usually at about 25-30 ° C which is cooled, for example, by means of sea water through heat-exchangers 14, and thereafter a second set of spray nozzles 15 for atomizing water at a temperature of 2-10 ° C which is cooled, for example, by means of refrigerating units 16.
  • the gas in the cooler 11 is cooled to a temperature which is a few degrees above the temperature of the cooling water, such as to 15 ° C if the temperature of the water is 10 ° C.
  • a temperature which is a few degrees above the temperature of the cooling water, such as to 15 ° C if the temperature of the water is 10 ° C.
  • all the tar and most of the naphthalene are condensed. Tar and naphthalene, swept down by the water, fall down onto the bottom of the tower together with the cooling water and the condensate of steam still contained in the gas, excepted those very fine particles that may be swept along by said gas.
  • This gas is then conveyed to the droplet remover 17 where it is deprived of those particles.
  • the refrigerating unit for the final cooling of the gas in the tower is regulated so as to minimize the energy consumption. If the gas is cooled to the temperature of 15 ° C, the amount of gaseous naphthalene in the gas is 0.25 g/Nm3, which amount generally causes no fouling problem in the pipes even if the temperature of the gas flowing through the network falls some degrees below said temperature. If the average temperatures in the pipes are above 15 ° C, the gas need not be cooled to said temperature, since naphthalene will not condense at all. Said possibility of regulating this unit allows a remarkable saving either of electric power required for operating the refrigerating unit if the latter is of the compression type, or of vapor if it is of the absorption type.
  • the water that collects on the bottom of the cooler 11 is conveyed through the piping 17 into a decantation-flotation tank 18, where the water that is captured in the cyclone 17 is also conveyed through the piping 19.
  • the materials lighter than water such as naphthalene flakes and foams, will float and the heavier materials, such as tar and anthracene oils, will settle onto the bottom.
  • the floating materials are removed from the surface through the piping 20, and the settled materials are removed from the bottom through the piping 21.
  • the two pipings 20 and 21 lead to a single piping 22 which conveys to the decanter 9 the mixture of tar, naphthalene and water being sucked together.
  • tar and naphthalene are closely in contact with each other, which is enhanced by the turbulence caused by the pump 30 and the speed of the fluid in the piping, said speed being maintained at suitable values.
  • the length of the piping 22, moreover, is such as to permit a nearly complete absorption of naphthalene into the tar. It is to be noted that, partially, such an absorption has occurred in the tower, during the cooling step, in the cyclone, in the piping conveying the fluids into the decanter, and said absorption is completed in said decanter.
  • ammoniacal water being removed from the surface in the decanter 9 therefore, is devoid of tar, which has all settled down onto the bottom, and of naphthalene, which has been completely absorbed by the tar.
  • Said water is re-cycled, and a fraction of it will be used for the first cooling step in the header, to which it is conveyed through the pipings 23, 24 and from which it resumes the cycle described above.
  • the remaining fraction of the water from the decanter 9 is conveyed to the cooling tower through the piping 26. It is first cooled by means of cooling water in the heat exchanger unit 14 to a temperature of about 25-30 ° C and it is partly sprayed through the nozzles 13 in the cooler, while the remaining portion is further cooled in the refrigerating unit 16 and is sprayed in said cooler through the nozzles 15.
  • a certain amount of water supplied to the decantation-flotation tank 18 by the cooler 11 and cyclone 17, is withdrawn through the pipings 20 and 21 together with tar and naphthalene, as stated above, but most of it is withdrawn at an intermediate level of the decantationflotation tank through the piping 27.
  • This water contains suspended therein very fine particles of tar and naphthalene such that they have not been able to move up to the surface or down to the bottom of the decantation-flotation tank. Said water is conveyed through the piping 27 to the bottom of the header 3.
  • the amount of tar may not be enough, in certain sections of the plant, to absorb, with sufficient rapidity, the condensed naphthalene in that section. Therefore, some tar is drawn off the sections where it is not saturated with naphthalene or, preferably, where it has a relatively low content of naphthalene, and is conveyed to other sections where naphthalene is to be absorbed.
  • a piping 28 is provided to withdraw tar from the bottom of the decanter 9 and to convey it to the bottom of the cooler 11 and, through a branch 29, into the piping 27.
  • the existing amount of tar or the naphthalene-saturated condition of tar are such as to either nullify the absorption of free naphthalene, or to permit it with insufficient rapidity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Industrial Gases (AREA)
  • Drying Of Gases (AREA)
  • Motor Or Generator Cooling System (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

1. Ein Verfahren zum Kühlen, Entfeuchten, Denaphthalisieren und Entteeren von Kohle-Destillationsgas, das aus einem Koksofen (1) austritt, bei dem:
- das genannte Gas von einer Temperatur von 700-900°C, die es beim Verlassen des Koksofens (1) hat, auf eine Temperatur von 80-90°C mittels Wasserstrahlen einer Temperatur von etwa 60-70°C im vertikalen Endabschnitt einer jeder der Leitungen (2) gekühlt wird, die das Gas von einem Ofen (1) zu dem Sammler (3) führen, in dem das gesamte Gas von einer Anlage gesammelt wird, um den den Sättigungsgrad bei dieser Temperatur übersteigenden Dampfanteil zu kondensieren und den meisten Teer und die meisten Anthrazenöle zu kondensieren, die sich in dem genannten Sammler (3) zusammen mit dem versprühten Kühlwasser sammeln, sowie eine kleine Fraktion von Naphthalin, das in dem Teer und den Anthrazenölen gelöst ist;
- das genannte Gas dann aus dem genannten Sammler, (3) in Leitungen strömt, wobei Wasser, Teer und Anthrazenöle zu einem Wasser-Gas-Separator (6) mitgeführt werden, in dem das genannte Gas von den genannten anderen Materialien getrennt wird und letztere dann in einem Dekantiergerät (9) gesammelt werden;
- Teer und Anthrazenöle durch Schwerkraft auf dem Boden des Dekantiergerätes (9) abgesetzt werden, wodurch das Wasser, auf diese Art und Weise von Teer und Anthrazenölen befreit, für das Verfahren wieder benutzt werden kann;
- das genannte Gas dann nach dem Separator (6), immer noch mit einer Temperatur von 80-90°C, zu einem Kühler (11) gelangt, üblicherweise des Kaltwasser-Sprühtyps, in dem Wasser mit der Temperatur von 2-30°C versprüht wird, um das Gas auf eine Temperatur von wenigen Grad über der des Wassers zu kühlen, um die Kondensation allen Teers und Naphthalins entsprechend deren Sättigung zu erreichen, die dann zu einem Dekantier-Flotations-Tank (18) zusammen mit dem Wasser das versprüht worden ist und dem, was infolge der genannten Temperaturreduktion kondensiert worden ist, gefördert wird;
- das genannte Gas dann zu einem Tröpfchen-Separator (17) gelangt, in dem die verbliebenen sehr feinen Partikel von Wasser, Teer und Naphthalin, die letzteren zwei dabei entweder in den genannten Tröpfchen inkorporiert oder nicht, getrennt und zu dem genannten Dekantier-Flotations-Tank (18) gefördert werden;
- das genannte Gas, auf diese Weise von Naphthalin und Teer befreit, dann in die Auslaßleitungen der Anlage eintritt, um weiter behandelt oder verwendet zu werden;
- die Anteile von Wasser, die Teer und Naphthalin beinhalten, die in den Dekantier-Flotations-Tank (18) von dem Kühler (11) und dem Tröpfchen-Separator (7) gefördert werden, darin verweilen, um es den Partikeln leichter als Wasser, im wesentlichen Naphthalin, zu ermöglichen, zur Oberfläche aufzuflottieren und um es den schwereren Partikeln, beispielsweise Teer, zu ermöglichen, sich auf dem Boden abzusetzen und das genannte Wasser dann von einer Zone etwa in einer mittleren Höhenlage des Dekantier-Flotations-Tankes (18) abgezogen wird und es ausschließlich Partikel beinhaltet, die dank ihrer sehr kleinen Abmessungen darin in Suspension verblieben sind;
- das genannte Wasser dann in den Boden des genannten Sammlers (3) gefördert wird, wo die Gasströme von den Koksöfen zusammengesammelt werden und sich mit dem Kühlwasser und dem den kondensierten Teer beinhaltenden Kondenswasser vereinigen;
- das Naphthalin, das in dem Kühler (11) kondensiert wird und in dem Tröpfchen-Separator (17) gesammelt wird, mit dem kondensierten Teer kontaktiert und dabei durch Lösung absorbiert wird, welche Absorption sukzessive in dem Kühler (11) und dem Tröpfchen-Separator (17), in der zu dem Dekantier-Flotations-Tank (18) führenden Leitung, in dem Dekantier-Flotations-Tank (18) und in der Leitung (27) von Letzterem zum Sammler (3), in dem Sammler, wo es den frischkondensierten Teer kontaktiert, in der nachfolgenden Leitung (5) von dem Sammler (3) zu dem WasserGas-Separator (6), in der folgenden Leitung (8) von dem Separator (6) zu dem Dekantiergerät (8) für den Teer und schließlich in dem Dekantiergerät (9) geschieht, in dem die Absorption von Naphthalin im Teer vervollständigt wird;
- das Naphthalin, das sich in dem Dekantier-Flotations-Tank (18) zur Oberfläche bewegt hat und der Teer, der sich auf dessen Boden abgesetzt hat, werden durch Oberflächenabschöpf- und Bodenauslaßleitungen (20, 21) zusammen mit einer vorgegebenen Menge Wasser entfernt und werden zusammen in einer Einzelleitung (22) zu der Teer-Dekantiervorrichtung (9) gefördert;
- während des Weges von dem Dekantier-Flotations-Tank (18) zu der Teer-Dekantiervorrichtung (8) Naphthalin und Teer innig miteinander kontaktieren, wodurch Naphthalin durch den Teer absorbiert wird und die Absorption in der Dekantiervorrichtung (9) fortgesetzt wird, bis sie vollständig vollzogen ist;
- das in der Dekantiervorrichtung (9) wiedergewonnene und nun von Naphthalin und Teer befreite Wasser teilweise für das Verfahren wieder benutzt wird.
2. Ein Verfahren gemäß Anspruch 1, bei dem auf das in dem genannten Kühler (11) zu kühlende Gas zunächst mit Sprühwasser (13) bei einer Temperatur von 25-30°C und dann mit Sprühwasser (15) mit einer Temperatur von 2-10°C eingewirkt wird.
3. Ein Verfahren nach den Ansprüchen 1 und 2, bei dem das bei einer Temperatur von 25-30°C versprühte Wasser (13) im Wärmetauscher mittels natürlich zur Verfügung stehendem Kühlwasser mit einer geringfügig geringeren Temperatur gekühlt wird und das bei 2-10°C versprühte Wasser (15) mittels Kühleinheiten (16) gekühlt wird, die ihrerseits mittels des genannten zur Verfügung stehenden Wassers gekühlt werden.
4. Ein Verfahren nach Anspruch 1 entweder allein oder in Kombination mit Anspruch 3, bei dem die Temperatur des Kühlwassers, das in dem Kühler (11) versprüht wird, über 10°C, bis zu 30°C liegt und das genannte Gas nur wenige Grade unterhalb der Umgebungstemperatur in dem Raum, in dem das Gas verteilt wird, oder auf die gleiche Temperatur gekühlt wird.
5. Ein Verfahren nach Anspruch 1 entweder allein oder in Kombination mit einem oder allen der Ansprüche 2-4, bei dem etwas von dem Teer, der in bestimmten Stufen des Verfahrens noch nicht mit Naphthalin gesättigt ist oder vorzugsweise einen niedrigen Gehalt an Naphthalin hat, abgezogen wird, wo diese Bedingungen gegeben sind und durch geeignete Leitungen zu anderen Stufen des Verfahrens gefördert wird, in denen es an Teer, der in der Lage ist, dort schnell Naphthalin zu absorbieren, fehlt, um so den Kontakt zwischen Naphthalin und dem genannten ungesättigten Teer zu begünstigen und auf diese Weise die Absorption des Naphthalins im Teer zu beschleunigen.
6. Ein Verfahren nach Anspruch 1 entweder alleine oder in Kombination mit einem oder mehreren der Ansprüche 2-5, bei dem mehr oder weniger stark turbulente Bewegungen in den Leitungen der Anlage erzeugt werden, indem man entweder auf die Geschwindigkeit der Strömungsmedien oder die Charakteristiken der Pumpen oder die Konfiguration der Leitungen einwirkt, um den Kontakt zwischen Teer und Naphthalin zu begünstigen und so in einem maximalen Ausmaß die Absorption von Naphthalin im Teer zu beschleunigen.
EP87106786A 1986-05-14 1987-05-11 Einrichtung zur Kühlung und zur Eliminierung von Feuchtigkeit, Naphtha und Tar von Kohlendestillationsgasen Expired - Lifetime EP0245814B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87106786T ATE49992T1 (de) 1986-05-14 1987-05-11 Einrichtung zur kuehlung und zur eliminierung von feuchtigkeit, naphtha und tar von kohlendestillationsgasen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT12476/86A IT1204163B (it) 1986-05-14 1986-05-14 Impianto di raffreddamento deumidificazione denaftalinizzazione e de catramazione del gas di distillazione del carbon fossile
IT1247686 1986-05-14

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Publication Number Publication Date
EP0245814A1 EP0245814A1 (de) 1987-11-19
EP0245814B1 true EP0245814B1 (de) 1990-01-31

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EP87106786A Expired - Lifetime EP0245814B1 (de) 1986-05-14 1987-05-11 Einrichtung zur Kühlung und zur Eliminierung von Feuchtigkeit, Naphtha und Tar von Kohlendestillationsgasen

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EP (1) EP0245814B1 (de)
AT (1) ATE49992T1 (de)
BR (1) BR8702440A (de)
DE (1) DE3761568D1 (de)
ES (1) ES2012468B3 (de)
IT (1) IT1204163B (de)

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Publication number Priority date Publication date Assignee Title
DE4439147A1 (de) * 1994-11-03 1996-05-09 Salzgitter Anlagenbau Verfahren und Anlage zur Behandlung industrieller Abwässer
CN101975402B (zh) * 2010-10-31 2012-08-29 湖北科伦药业有限公司 锅炉燃烧节能减排系统
CN108069155A (zh) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 一种储罐排放气减排及回收系统
CN110559803A (zh) * 2019-10-11 2019-12-13 武汉三立鼎兴科技有限公司 一种含萘废气处理系统及其处理方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451896A (en) * 1967-04-07 1969-06-24 Otto Construction Corp Method of cleaning a stream of coke oven gas and apparatus therefor
DE2632092A1 (de) * 1976-07-16 1978-01-26 Otto & Co Gmbh Dr C Verfahren zum kuehlen von gasen, die feststoffe, teer und naphthalin enthalten
US4239511A (en) * 1978-12-14 1980-12-16 Krupp-Koppers Gmbh Process and apparatus for cooling coke oven gas

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EP0245814A1 (de) 1987-11-19
ES2012468B3 (es) 1990-04-01
IT1204163B (it) 1989-03-01
IT8612476A0 (it) 1986-05-14
ATE49992T1 (de) 1990-02-15
BR8702440A (pt) 1988-02-23
DE3761568D1 (de) 1990-03-08

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