EP0245814B1 - Installation pour refroidir, déshumidifier, dénaphter et dégoudronner les gaz de distillation de charbon - Google Patents

Installation pour refroidir, déshumidifier, dénaphter et dégoudronner les gaz de distillation de charbon 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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Expired - Lifetime
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EP87106786A
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German (de)
English (en)
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EP0245814A1 (fr
Inventor
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)
  • Industrial Gases (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Motor Or Generator Cooling System (AREA)
  • Drying Of Gases (AREA)

Claims (6)

1. Procédé de refroidissement, de déshumidifica- tion, de dénaphténisation et de dégoudronnage pour un gaz de distillation de houille sortant de fours à coke (1), dans lequel:
- le gaz susdit est refroidi depuis la température de 700 à 900°C qu'il présente en sortant des fours à coke (1) jusqu'à une température de 80-90°C, grâce à des pulvérisations d'eau à la température d'environ 60-70°C dans la partie verticale terminale de chacune des canalisations (2) menant le gaz depuis un four (1) vers le collecteur (3), où tout le gaz d'un ensemble est récolté de manière à condenser la vapeur d'eau dépassant le degré de saturation à cette température et à condenser la plus grande partie du goudron et des huiles anthracéniques qui se récoltent dans le collecteur susdit (3), en même temps que l'eau de refroidissement qui est pulvérisée, et une petite fraction de naphtalène qui se dissout dans le goudron et les huiles anthracéniques;
- le gaz susdit sort ensuite du collecteur (3) pour aller dans les canalisations, emmenant l'eau, le goudron et les huiles anthracéniques vers un séparateur d'eau/gaz (6), où le gaz est séparé des autres matières susdites et ces dernières sont ensuite récoltées dans un décanteur (9);
- le goudron et les huiles anthracéniques se déposent sous l'effet de la pesanteur sur le fond du décanteur (9), de sorte que l'eau, ainsi débarrassée du goudron et des huiles anthracéniques, peut être réutilisée pour le procédé;
- le gaz susdit passe ensuite par le séparateur (6), toujours à la température de 80-90°C, vers un appareil de refroidissement (11), habituellement du type à pulvérisation d'eau froide, où l'eau se trouvant à une température de 2 à 30°C est pulvérisée pour refroidir le gaz jusqu'à une température de quelques degrés au-dessus de celle de l'eau, de manière à obtenir la condensation de la totalité du goudron et du naphtalène, correspondant à leur saturation, qui seront transférés à une réservoir de décantation-flottation (18) en même temps que l'eau qui a été pulvérisée et qui a été condensée à la suite de la réduction de température;
- le gaz susdit passe ensuite par un séparateur de gouttelettes (17), où les très fines gouttelettes restantes d'eau, le goudron et le naphtalène, ces deux derniers étant incorporés ou non dans ces gouttelettes, sont séparés et transférés au rése- voir de décantation-flottation (18);
- le gaz susdit, ainsi débarrassé du naphtalène et du goudron, pénètre ensuite dans les canalisations de sortie de l'installation pour être encore traité ou utilisé;
- les quantités d'eau contenant du goudron et du naphtalène, qui sont envoyées dans le réservoir de décantation-flottation (18) depuis l'appareil de refroidissement (11) et le séparateur de gouttelettes (17) y séjourneront pour permettre aux particules plus légères que l'eau, essentiellement du naphtalène, de flotter à la surface, et pour permettre aux particules plus lourdes, c'est-à-dire le goudron, de se déposer sur le fond, cette eau étant ensuite retirée d'une zone se situant à peu près à un niveau intermédiaire du réservoir de décantation-flottation (18) et ne contenant que des particules qui y sont restées en suspension du fait de leurs dimensions très petites;
- l'eau susdite est ensuite transférée dans le fond du collecteur (3), où les débits de gaz des fours à coke se rassemblent, et elle rejoint l'eau de refroidissement et l'eau de condensation contenant le goudron condensé;
- le naphtalène qui est condensé dans l'appareil de réfrigération (11) et est récolté dans le séparateur de gouttelettes (17) entre en contact avec le goudron condensé et y est absorbé par dissolution, cette absorption se produisant successivement dans l'appareil de refroidissement (11) et dans le séparateur de gouttelettes (17), dans la canalisation menant au réservoir de décantation-flottation (18), dans le réservoir de décantation-flottation (18), dans la canalisation (27) partant de ce dernier vers le collecteur (3), dans le collecteur où elle entre en contact avec le goudron fraîchement condensé, dans la canalisation suivante (5) partant du collecteur (3) pour aller vers le séparateur d'eau/gaz (6), dans la canalisation suivante (8) partant du séparateur (6) allant ves le décanteur (9) de goudron, et finalement dans le décanteur (9), où l'absorption de naphtalène dans le goudron est achevée;
- le naphtalène qui s'est déplacé jusqu'à la surface du réservoir de décantation-flottation (18) et le goudron qui s'est déposé sur le fond de ce réservoir sont séparés par des conduits d'écrémage de surface et de décharge de fond (20, 21 ), en même temps qu'une certaine quantité d'eau, et ils sont transférés vers une seule canalisation (22) en direction du décanteur de goudron (9);
- durant le déplacement depuis le réservoir de décantation-flottation (18) vers le décanteur de goudron (9), le naphtalène et le goudron entrent en contact intime entre eux, de sorte que le naphtalène sera absorbé par le goudron, l'absorption étant ensuite poursuivie dans le décanteur (9) jusqu'à ce qu'elle soit complète;
- l'eau récupérée dans le décanteur (9) et à ce moment dépourvue de naphtalène et de goudron est partiellement réutilisée pour le procédé de l'invention.
2. Procédé suivant la revendication 1, dans lequel le gaz qui est refroidi dans l'appareil de refroidissement (11) reçoit d'abord l'action d'une eau pulvérisée (13) à une température de 25-30°C, et ensuite d'une eau pulvérisée (15) à une température de 2-10°C.
3. Procédé suivant les revendications 1 et 2, dans lequel l'eau (13) qui est pulvérisée à une température de 25-30°C est refroidie dans des échangeurs de chaleur grâce à de l'eau de refroidissement disponible naturellement à une température légèrement inférieure, et l'eau (15) qui est vaporisée à 2-10°C est refroidie grâce à des unités de réfrigération (16) qui, à leur tour, sont refroidies par l'eau disponible susdite.
4. Procédé suivant la revendication 1 considérée seule ou en combinaison avec la revendication 3, dans lequel la température de l'eau de refroidissement qui est pulvérisée dans l'appareil de refroidissement (11) est supérieure à 10°C, en allant jusqu'à 30°C, et le gaz est refroidi de quelques degrés seulement en dessous de la température ambiante dans l'espace où ce gaz est distribué, ou bien à la même température.
5. Procédé suivant la revendication 1, considérée seule ou en combinaison avec l'une quelconque des revendications 2 à 4, dans lequel une certaine partie du goudron qui, dans certaines étapes du procédé, n'est pas encore saturée de naphtalène ou présente de préférence une aible teneur de naphtalène, est soutirée là où de telles conditions se présentent et elle est transférée, par des canalisations appropriées, vers d'autres étapes du procédé, qui manquent de goudron capable d'absorber facilement le naphtalène, de manière à renforcer le contact entre le naphtalène et ce goudron insaturé et à accélérer ainsi l'absorption de naphtalène dans le goudron.
6. Procédé suivant la revendication 1, considérée seule ou en combinaison avec une ou plusieurs des revendications 2 à 5, caractérisé en ce que des mouvements turbulents plus ou moins importants sont créés à l'intérieur des canalisations de l'installation en agissant sur la vitesse des fluides, ou sur les caractéristiques des pompes, ou sur la configuration des canalisations, etc., de manière à renforcer le contact entre le goudron et le naphtalène et à accélérer ainsi, à un degré maximum, l'absorption du naphtalène dans le goudron.
EP87106786A 1986-05-14 1987-05-11 Installation pour refroidir, déshumidifier, dénaphter et dégoudronner les gaz de distillation de charbon Expired - Lifetime EP0245814B1 (fr)

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
IT1247686 1986-05-14
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

Publications (2)

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

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EP87106786A Expired - Lifetime EP0245814B1 (fr) 1986-05-14 1987-05-11 Installation pour refroidir, déshumidifier, dénaphter et dégoudronner les gaz de distillation de charbon

Country Status (6)

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

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* Cited by examiner, † Cited by third party
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

Family Cites Families (3)

* 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

Also Published As

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

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