WO2008015487A1 - Procédé et appareil de nettoyage des gaz de combustion - Google Patents

Procédé et appareil de nettoyage des gaz de combustion Download PDF

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Publication number
WO2008015487A1
WO2008015487A1 PCT/IB2006/002106 IB2006002106W WO2008015487A1 WO 2008015487 A1 WO2008015487 A1 WO 2008015487A1 IB 2006002106 W IB2006002106 W IB 2006002106W WO 2008015487 A1 WO2008015487 A1 WO 2008015487A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat transfer
condensate
outlet
gases
water
Prior art date
Application number
PCT/IB2006/002106
Other languages
English (en)
Inventor
Jerzy Chomiak
Original Assignee
Jerzy Chomiak
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jerzy Chomiak filed Critical Jerzy Chomiak
Priority to PCT/IB2006/002106 priority Critical patent/WO2008015487A1/fr
Publication of WO2008015487A1 publication Critical patent/WO2008015487A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device

Definitions

  • the present invention relates to a method and apparatus for cleaning combustion gases, in particular combustion gases of marine diesel engines and small liquid fuel power plants,
  • the method by eliminating deposit forming and corrosive constituents of the gases, allows exhaust gas re-circulation (EGR) to control emissions of nitrogen oxides and prevents visible condensation plume formation at the stack without need to reheat the gases
  • the problem is that the ship engines may be considered to be some sort of incinerators, which burn the otherwise useless residual hydrocarbons and in the waste majority of cases ships have just one fuel tank and are unable to carry fuels of different qualities, Even if in some cases the possibility exists, switching from one fuel to another requires modifications of the fuel and oil systems, mixing compatibility of the fuels to avoid pump seizure, as well as development of special switching routines for the fuel and oil, specific to each engine, not yet available, Other problems are the low availability of high quality fuels particularly in remote regions and the large price differentials between high and low quality fuels typically exceeding the 30 % level.
  • Seawater is a weak base with considerable acid buffering capacity so the concept of using it to wash the exhaust gases using a scrubber comes immediately to ones mind as the preferred solution of the problem of removing and neutralizing the sulfur oxides which react with water to form sulfuric (H 2 SO 4 ) and sulfurous acid (H2SO3), Indeed seawater scrubbers for land-based power plants became popular after the development by ABB Environmental in Norway and Norsk-Hydro of the Flakt-Hydro process in the 1970-ties as described in the well known paper by Stromnen, S, O and Hjelm, F.: "Sulfur in Fuel Gases can Safely be Absorbed by Seawater and Returned Iu Oceans", ICHEME Symposium Series No 131 pp 95-108, 1993.
  • seawater based scrubber facilities for power plants are offered by many companies.
  • the systems offered use electrostatic precipitators to remove PM before the scrubber, intense reheat of exhaust after scrubber to avoid visible condensation plume formation at the stack and extensive discharge water cleaning facilities.
  • Few data are available regarding the details of the processes but it is known that large amounts of seawater are used for the washing in the range often exceeding 15 kg per Nm 3 of the gases, which makes water cleaning a problem.
  • the first commercial applications of exhaust gas seawater scrubbers in the marine industry were introduced not as an answer to today emissions control problems but. as means to generate inert gas for oil tankers to fill air space in cargo tanks to prevent hydrocarbon vapor explosions.
  • the first such systems appeared in 1930's and their installation became common since 1970's. Many companies supply the systems.
  • the scrubber unit is combining three scrubbing principles, a high energy, large pressure drop Venturi scrubber, a wet filter and a spray section, for high-efficiency cooling and cleaning the gases. Concentric arrangement with a demister section and a mesh type wet filter gives independence of ships pitching and rolling without loss of efficiency. However, soot-blowing devices are also included in the units, which shows that deposit formation is a problem.
  • the system uses about 15 kg of water per Nm 3 of gas and produces gases having a temperature of 5 0 C above seawater temperature and 100 % humidity. SOz is reduced in the system from typically 3000 ppm to less than 100 ppm and soot extraction equal to 99 % but just for particles larger than 1 micrometer is claimed.
  • the film flow in the condenser separates the condensable liquids from the exhaust gas in such a way that outside the film the gas has much higher temperatures and is dry which prevents condensational plume formation when the gas is released into atmosphere without need of reheating.
  • Yet another object of the present invention is to provide an integrated evaporator-condenser combination operating over a large flow rate range and in particular allowing high gas flow rates with minimal pressure losses.
  • ⁇ still further object of the invention is to provide an evaporator-condenser combination for gas cleaning which does not require reheating of the gas to avoid condensation plume formation in the atmosphere.
  • Another object of the invention is to provide an evaporator-condenser combination composed of large number of identical tubes where precise dosage of neutralizing chemicals to the liquid film can be realized
  • a still further object of the invention is to provide an evaporator-condenser combination based on tested technology, insensitive to ship movements, which can easily be accepted by the classification societies for installation onboard ships.
  • a method for cleaning combustion gases comprising the steps of: introducing exhaust gases containing sulfur oxides, unburned hydrocarbons and solid particulate matter into a heat exchanger comprising at least one heat transfer surface, preferably in form of a tube, having an evaporator section and a condenser section integrated with each other; spraying a neutralizing solution in water onto said at least one heat transfer surface at a rate proportional to the exhaust gas flow rate being introduced into said heat exchanger; evaporating at least portion of the neutralizing solution in said evaporating section to allow at least a portion of sulfur oxides and nitrogen dioxide to react with water vapor to form acidic gases; condensing said acidic gases and unburned hydrocarbon vapor in form of a condensate film, which deposes on said heat transfer surface in said condenser section, reacts further with the neutralizing alkaline components, absorb
  • the apparatus according to the invention is preferably composed of a bundle of open pipes resembling a smoke tube boiler, where the cleaned gases flow downwards and the temperature controlling water upwards and where the condensate collected at the bottom is partially re- circulated and injected at the top after addition of acid neutralizing chemicals, to be partially evaporated to enhance the gas cleaning processes. Both evaporation and condensation occur in a falling film mode and the film is used for absorption of remaining SOj. Absorption of COs is prevented and absorption of SOj maximized by keeping the pH of the condensate at the bottom of the apparatus close to 6-6.5.
  • the method and apparatus according to the invention by eliminating condensing, deposit forming and corrosive constituents of the gases, allows exhaust gas re-circulation (EGR) to control emissions of nitrogen oxides and prevents visible condensation plume formation at the stack without reheating the gases.
  • EGR exhaust gas re-circulation
  • Fig, 1 is a schematic partially broken away side view of the exemplary apparatus for cleaning combustion gases with integrated evaporator-condenser sections taken in direction of arrows I-I of Fig 2;
  • Fig. 2 is a schematic partially broken away top view of the apparatus of Fig, 1 taken in direction of arrows H-Il;
  • Fig 3 shows schematically an experimental apparatus in which experiments on the method according to the present invention have been carried out, atid
  • Fig, 4 is a closer sectional view "A" of Fig. 3 showing the condenser section exit on a relatively large scale presenting the gas and liquid film separation step according to the invention, Best Mode of Carrying Out the Invention
  • the basis of the present invention is the observation that the key process in cleaning combustion gases, in particular exhaust emission abatement for diesel engines and small power plants using low quality fuels, is to increase water contents (humidity) of the exhaust gases and then it removal by condensation, which moves the pollutants from gas into a liquid film.
  • the process is realized in flow separation free heat exchangers ex. cooled tubes, utilizing two very effective methods; film evaporation and film condensation.
  • the water needed for the gas treatment is obtained from re- circulation of the condensate or filtered water supply ex, seawater preheated in the apparatus.
  • evaporation and condensation enhances all the liquid-gas mass transfer and reaction processes including capture of solid particles and droplets formed by bulk condensation which are deposited in the condensation films by the ⁇ nophoresis, diffusiophoresis and Stefan flow generated by the condensation, capture of SO3 and NOj, which after reaction with water vapor to form gaseous acids condense to contribute to the film formation, capture of unburned hydrocarbons by parallel condensation, and finally capture of SO 2 by absorption in the condensate film.
  • neutralizing alkaline additives in the form of ex sodium hydroxide (caustic soda) or sodium carbonate (ash soda) solutions in water are added to the condensate or process water.
  • the apparatus comprises an exhaust gas inlet 1 through which the exhaust gas enters the apparatus and exhaust gas outlet 2 through which said gas exits the apparatus.
  • ⁇ number of heat transfer surfaces 3 in form of preferably vertical tubes 4 are located between the exhaust gas inlet 1 and the clean exhaust gas outlet 2 to form the heat exchanger of the apparatus.
  • the heat exchanger is located in a housing 5 through which a cooling water 6 flow is realized.
  • the housing 5 is provided wkh water inlet 7 located at the bottom of the heat exchanger connected to a water pump 8 and with a high flow rate outlet 9 placed in the upper part of the housing 5, as well as a low flow rate water outlet 10 located above the high flow rate water outlet 9.
  • Each heat transfer surface 3 is divided into two integrated sections: evaporator section 1 ⁇ and condenser section 12 being parts of the same vertical tube 4.
  • the division of heat transfers surfaces 3 into evaporator section I t and condenser section 12 is realized by the rate of cooling water flow - higher in the condenser section 12 and tower in the evaporator section . 1
  • the evaporator section 1 1 is formed between the high flow rate outlet 9 and the low flow rate outlet 10 and the condenser section are placed below the evaporator section 11 ,
  • Means for separating the purified gas and the condensate are located at the bottom of the heat exchanger.
  • Said means for separating the gas and condensate comprises an exhaust gas tube 22, a condenser section surface 20 for depositing condensate film being situated coaxially with the exhaust gas tube 22.
  • said means for separating comprises an accumulator 13 for collecting the condensate film 19 exiting the condenser section 12 of the heat transfer surfaces 3 being situated below said condenser section surface 20.
  • the diameter of said exhaust gas tube 22 is smaller than the diameter of said deposing surface 20 at least twice the thickness of the condensate film 19 to allow it to flow down to the accumulator 13 (shown the best on Fig. 4).
  • the accumulator 13 is connected with a duct 14 provided with a pump 15 to discharge part of the condensate from the accumulator 13 and circulate it to the spray system of the apparatus.
  • the surplus condensate is removed for cleaning or disposal via the duct 17.
  • the duct 14 may be connected with the low flow rate outlet 10 via a water duct 23 to add heated cooling water to the concentrated neutralizing supplement before it is sprayed onto heat transfer surfaces 3.
  • the heated water duct 23 is provided with a valve 24 to control the portion of the water to be added into the duct 14, if it is required, without disturbing the outflow of the heated cooling water from the evaporator section of the apparatus.
  • the spray system comprises a collection, of nozzles 16 adapted for spraying an alkaline neutralizing solution, such as ex sodium hydroxide or sodium carbonate, onto the heat transfer surface 3 with a rate proportional to the gas flow rate.
  • the duct 14 has a condensate outlet 17 via which the surplus condensate is drained for cleaning and disposal, as well as it is provided with a neutralizing solution inlet 18 through which the concentrated supplement is admitted in response to a signal from a control system when. pH of the condensate drops below a predetermined level.
  • the method of cleaning combustion gases, according to the invention is the following.
  • the exhaust gas enters the apparatus via an inlet 1 and then flows over a number of heat transfer surfaces 3 in form of preferably vertical tubes before exiting from the outlet 2.
  • diluted alkaline neutralizing solution streams il, i2... containing, ex. sodium hydroxide or sodium carbonate, are sprayed through a collection of nozzles 16 onto the heat transfer surface 3 with a rate proportional to the gas flow rate and are first partially evaporated in the evaporator section 11 and then condensed in the condenser section 12,
  • the acidic gases SO3 and NO2 react with water vapor and then condense, dissociate and react with the neutralizing basic components and are removed with the condensate.
  • the alkaline condensate absorbs also and removes SO 2 front the gases, In parallel unburned hydrocarbons condense, are captured by the condensate film and removed from the gas, At the same time thermophoresis, diffusiophorests and Stefan flow induced by the condensation cause deposition of solid particulate matter (soot, ash) carried by the gas and fog droplets of condensable material formed by bulk condensation on the condensation films 19 (see Fig, 4) flowing along the condenser surfaces 20.
  • the temperature of the condenser section 12 of the heat transfer surfaces 3 should be kept well below the dew point temperature of the condensing vapors preferably more than 25K below the dew point,
  • the condensate exiting the heat transfer surfaces 3 of the condenser is collected in an accumulator 13.
  • the accumulator 13 serves as a buffer for the condensate circulation returning the condensate to the inlet of the apparatus to maintain a constant flow rate of the liquid through the system
  • the condensate passes through a duct 14 to which the concentrated alkaline supplement is admitted through the inlet 18.
  • the pH of the solution in the accumulator 13 is controlled, As the acidic gases enter into the condensate and react with the neutralizing alkaline additives the pH of the condensate drops.
  • a control system admits more of the concentrated alkaline solution to the spray system via the inlet 18,
  • a portion of the cooling water taken from the hot water outlet of the evaporator section 10 may be used for spraying of the neutralizing additives and enhancement of humidity of the exhaust gases. This can be preferred in marine application where arbitrary quantities of alkaline seawater are available able to reduce the use of neutralizing chemicals.
  • the division of the heat transfers surfaces 3 into evaporator sections 11 and condenser sections 12 is realized by the rate of cooling water flow-
  • the cooling water 6 is admitted at the bottom of the heat exchanger via the water inlet 7 and it main part is released at the beginning of the condenser section 12 through the high flow rate outlet 9. A much smaller portion is released at the entrance of the evaporator section 11 through the low flow rate outlet 10
  • the water entering the apparatus has typically a temperature of about 10-15 ⁇ C
  • the temperature increases in the condenser section 12 to about 20-25 0 C Temperatures below 71°C should be kept in the evaporator section 11 to avoid scale formation.
  • the evaporator section 1 between the outlets 9 and 10, produces surplus heat as the gases entering the apparatus have typically ISO 0 C.
  • the heat is of high enough quality to be effectively utilized, Exactly the same functions of all the elements are realized in the test apparatus, Fig. 3.
  • the nozzle 16 in form of swirl or multi-orifice atomizer is used in this case to distribute the alkaline solution on the evaporator surface. Admission of the exhaust gas through a number of flow restricting orifices 21 assures uniform gas flow distribution across the inlet of the apparatus.
  • the separator is preferably in form of a skimmer i.e. an exhaust gas tube 22 that is large enough to accept the gas but not the condensate film 19 flowing along the condenser section surfaces 20,
  • a skimmer i.e. an exhaust gas tube 22 that is large enough to accept the gas but not the condensate film 19 flowing along the condenser section surfaces 20,
  • other water separator types can be used,
  • the gas streams j 1 , j2.. , . leaving the condenser section 12 have a much higher temperature, than the liquid condensate film 19, and they are dry because most of the condensable components of the exhaust gases are captured in the film, thus the gas does not require reheating to avoid condensation in the exhaust plume, producing visible exhaust at the stack.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé et un appareil de nettoyage des gaz de combustion, en particulier des gaz de combustion de moteurs diesel marins et de petites centrales énergétiques à combustible liquide. Le procédé comprend les étapes consistant à : introduire des gaz d'échappement dans un appareil possédant un échangeur thermique comprenant au moins une surface de transfert thermique (3), de préférence sous forme de tube (4), possédant une section d'évaporateur (11) et une section de condenseur (12) intégrées l'une à l'autre; pulvériser une solution de neutralisation dans l'eau ou un condensat remis en circulation au moyen de buses (16) sur ladite surface de transfert thermique (3) à un débit proportionnel au débit de gaz; évaporer une partie de la solution de neutralisation dans ladite section d'évaporation (11) pour permettre au moins à une partie des gaz acides de réagir avec la vapeur d'eau; condenser des vapeurs contenues dans les gaz d'échappement sous forme de film de condensat qui se dépose sur ladite surface de transfert thermique (3) dans ladite section condenseur (12); extraire, séparément des gaz d'échappement épurés, ledit film de condensat sortant de la surface de transfert thermique (3), le diriger vers un accumulateur (13) et le mettre en circulation pour pulvériser ladite solution de neutralisation, et décharger les gaz d'échappement épurés et le condensat en surplus provenant du traitement. En variante, pour pulvériser ladite solution de neutralisation, on peut utiliser une eau chauffée provenant de la sortie (10). La division des surfaces de transfert thermique (3) en sections d'évaporateur (11) et de condenseur (12) est assurée par le débit d'écoulement d'eau de refroidissement admis au fond de l'échangeur thermique, une partie principale de l'eau de refroidissement étant libérée au début de la section de condenseur (12, sortie 9) et une partie beaucoup plus petite d'eau étant libérée à l'entrée de la section d'évaporateur (11, sortie 10).
PCT/IB2006/002106 2006-08-01 2006-08-01 Procédé et appareil de nettoyage des gaz de combustion WO2008015487A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2006/002106 WO2008015487A1 (fr) 2006-08-01 2006-08-01 Procédé et appareil de nettoyage des gaz de combustion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2006/002106 WO2008015487A1 (fr) 2006-08-01 2006-08-01 Procédé et appareil de nettoyage des gaz de combustion

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2574393A1 (fr) 2011-09-30 2013-04-03 Alfa Laval Aalborg A/S Système de lavage et procédé
US9694317B2 (en) 2012-05-03 2017-07-04 Altira Technology Fund V L.P. Multi-pollutant abatement device and method
US9982582B2 (en) 2013-03-08 2018-05-29 Alfa Laval Corporate Ab Cleaning system and method for reduction of SOx in exhaust gases
CN112128791A (zh) * 2020-09-14 2020-12-25 张斯瑞 一种燃气锅炉排烟深度余热回收方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3303475A1 (de) * 1983-02-02 1984-08-02 Christian 8251 St Wolfgang Numberger Verfahren und vorrichtung zur reinigung von rauchgas und ruechgewinnung von abgaswaerme
DE4304192A1 (de) * 1993-02-12 1994-08-18 Noell Gmbh Verfahren zum Auswaschen der sauren Gaskomponenten aus Rauchgasen durch Absorption
US5707426A (en) * 1996-02-13 1998-01-13 The Babcock & Wilcox Company Key advanced linear kinetic absorber method using a particulate arresting device
US5843214A (en) * 1995-10-31 1998-12-01 California Energy Commission Condensable vapor capture and recovery in industrial applications

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3303475A1 (de) * 1983-02-02 1984-08-02 Christian 8251 St Wolfgang Numberger Verfahren und vorrichtung zur reinigung von rauchgas und ruechgewinnung von abgaswaerme
DE4304192A1 (de) * 1993-02-12 1994-08-18 Noell Gmbh Verfahren zum Auswaschen der sauren Gaskomponenten aus Rauchgasen durch Absorption
US5843214A (en) * 1995-10-31 1998-12-01 California Energy Commission Condensable vapor capture and recovery in industrial applications
US5707426A (en) * 1996-02-13 1998-01-13 The Babcock & Wilcox Company Key advanced linear kinetic absorber method using a particulate arresting device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2574393A1 (fr) 2011-09-30 2013-04-03 Alfa Laval Aalborg A/S Système de lavage et procédé
WO2013045272A1 (fr) 2011-09-30 2013-04-04 Alfa Laval Corporate Ab Système d'épuration et procédé
US9040005B2 (en) 2011-09-30 2015-05-26 Alfa Laval Corporate Ab Scrubber system and method
US9694317B2 (en) 2012-05-03 2017-07-04 Altira Technology Fund V L.P. Multi-pollutant abatement device and method
US9982582B2 (en) 2013-03-08 2018-05-29 Alfa Laval Corporate Ab Cleaning system and method for reduction of SOx in exhaust gases
CN112128791A (zh) * 2020-09-14 2020-12-25 张斯瑞 一种燃气锅炉排烟深度余热回收方法

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