• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the treatment of fumes comprising sulfur oxides and nitrogen oxides, the process comprising the following steps: - cooling of the fumes at the exit of the furnace, - contacting the fumes with a sulfur oxide neutralization agent, - separation of sulfur oxide residues and fumes, - heating of at least a part of the fumes separated from the sulfur oxide residues, - injection of a nitrogen oxide neutralization agent into the heated fumes, contacting the fumes and the agent for neutralizing the nitrogen oxides with a catalyst for reducing the nitrogen oxides, the process being characterized in that the cooling of the fumes at the outlet of the furnace is achieved by heating at least a part of the fumes separated from the sulfur oxide residues within the same heat exchanger (1).
    公开号:FR3044934A1
    申请号:FR1562130
    申请日:2015-12-10
    公开日:2017-06-16
    发明作者:Thierry Allegrucci；Chin Lim；Philippe Martineau
    申请人:Fives Solios Inc；Fives Solios SA；
    IPC主号:
    专利说明:

    The present invention relates to a treatment method for the pollutants contained in the fumes. In particular, the technology presented here consists in particular of treating the sulfur oxides - by a so-called desulfurization process (DeSOx) - such as sulfur dioxide (SO 2), and nitrogen oxides - by a process known as denitrification ( DeNOx) -, such as nitrogen oxide (NO) and nitrogen dioxide (NO2). The fumes to be treated come mainly from combustion sources such as coal boilers, or a calcination process for the production of cement, the production of lime, or any other calcination process.
    Such fumes contain one or more acid pollutants such as hydrochloric acid (HCl), hydrofluoric acid (HF), sulfur oxides (SOx) and nitrogen oxides (NOx), which can cause damage to the environment, for example by acid rain, if these fumes are released into the atmosphere without appropriate and effective treatment. Thus, it is essential to have a process that ensures efficient capture of these pollutants in order to comply with environmental regulations.
    Different technologies are known for desulfurization and denitrification. However, these technologies are generally only effective for one pollutant (SOx or NOx) since the process parameters required to treat SOx and NOx are different, among other things the temperature for their neutralization.
    To treat sulfur dioxide (SO 2), a widespread technology is the so-called semi-wet process, which consists in putting a lime-milk, dispersed in the form of droplets, in contact with the fumes in a reactor or in a cooling tower before their passage in a bag filter. However, this technology requires lowering the flue gas temperature very close to the dew point of the gases, in order to effectively capture the SO2. This leads to high water evaporation, high cost installations and increased risk of gas condensation.
    In the case of NOx treatment, two technologies are well known: SCR and SNCR. Both technologies use ammonia as a reagent. The SCR (Selective Catalytic Reduction) technology uses a catalyst which then allows the neutralization of NOx at average temperatures (around 350 ° C), either in a reactor or in a filter. The possible problem with this technology is the contamination of the catalyst over time because of the presence of SOx in the fumes, forcing its replacement after two or three years of operation. As for the SNCR (Selective Non-Catalytic Reduction) technology, it consists in the neutralization of NOx at very high temperatures, around 850 ° C - 1000 ° C, so that a catalyst is not necessary, but this which is sometimes incompatible with the process. In addition, the NOx reduction efficiency decreases significantly if the temperature range at the point of injection of the reagent is not respected. Finally, the injection of excess ammonia into the reactor can cause corrosion to downstream equipment and ammonia leakage into the environment.
    The required temperature range for SNCR technology is incompatible with that for desulphurisation. Therefore, SCR technology is preferred to combine it within a single plant with desulfurization. In addition, in order to prevent SOx from contaminating the NOx neutralization catalyst, desulfurization is generally performed prior to denitrification, so that fumes at a temperature suitable for desulphurization must be reheated prior to denitrification, involves energy consumption increasing the costs of the flue gas treatment process.
    EP 2 815 801 describes an example of such an installation, in which fumes generated in a boiler are sent firstly to an SO 2 treatment unit, then to an SCR processing unit. Between the two units, a compressor makes it possible to increase the temperature of the gases at the inlet of the treatment unit SCR.
    Such an installation is not entirely satisfactory, in particular because it requires a significant energy consumption to be able to change the temperature of the fumes. Indeed, at the outlet of the boiler, the temperature of the fumes depends on the nature of the process within the boiler - which can reach 1200 ° C. The flue gases must be cooled before entering the SO2 treatment unit and then reheated before entering the SCR treatment unit.
    There is therefore a need for a new treatment process that makes it possible in particular to ensure the good reduction efficiency of SOx and NOx pollutants by the same treatment system while overcoming the problems of known processes. For this purpose, according to a first aspect, the invention provides a method of treating flue gases from a combustion or calcination furnace comprising polluting species including sulfur oxides and nitrogen oxides. The process comprises the steps of: cooling the fumes at the furnace exit, contacting the fumes with a sulfur oxide neutralizing agent to obtain sulfur oxide residues, separating the sulfur oxide residues and fumes, heating at least a portion of the fumes separated from the sulfur oxide residues, injecting a nitrogen oxide neutralization agent into the heated fumes, contacting the fumes and the neutralization agent with nitrogen oxides with a catalyst to reduce nitrogen oxides.
    The cooling of the fumes at the outlet of the furnace is advantageously achieved by heating at least a portion of the fumes separated from the sulfur oxide residues within a same heat exchanger.
    The process thus makes it possible to clean the fumes of both sulfur oxides and nitrogen oxides in a single installation, while minimizing energy expenditure.
    According to one embodiment, the fumes after the injection of the nitrogen oxide neutralizing agent are mixed with the fumes after contact with the sulfur oxide neutralization agent. The separation of the sulfur oxide residues and the contacting with a catalyst are then carried out within the same separation device. The installation to carry out the process is thus of reduced size. The sulfur oxide neutralization agent is, for example, lime.
    According to one embodiment, when the fumes are brought into contact with the sulfur oxide neutralization agent, the humidity in the fumes is controlled in order to optimize the desulfurization.
    Part of the sulfur oxide residues may advantageously be recycled as a sulfur oxide neutralization agent.
    According to a second aspect, the invention proposes a flue gas treatment plant for implementing the method as presented above. The installation comprises an oven-connected heat exchanger for cooling the exhaust gases from the furnace, a desulphurization reactor connected to the heat exchanger and wherein the cooled flue gases are brought into contact with the oxidation neutralization agent. sulfur, a device for separating sulfur oxide residues and fumes, an injector for the nitrogen oxide neutralizing agent, and a catalytic device for denitrification. The separation device of the sulfur oxide residues is connected to the heat exchanger so that the fumes from the sulfur oxide residue separation device are heated by the fumes exiting the furnace.
    The device for separating the sulfur oxide residues and the catalytic device may advantageously be combined into one and the same separation device. The fumes after the injection of the nitrogen oxide neutralizing agent are then mixed in a filter inlet duct with the fumes exiting the reactor.
    The separation device comprises for example at least one bag filter, a catalyst for denitrification being distributed over the surface of the filter sleeves. Alternatively, the separation device comprises at least one baghouse filter, a catalyst for denitrification being placed inside the filter sleeves. Other advantages and characteristics will become apparent in the light of the description of an embodiment of an installation for implementing the treatment method according to the invention, accompanied by the figure which shows schematically the embodiment of the invention. .
    In the single figure, there is shown an installation 100 for the implementation of a method for treating flue gases from a combustion or calcination furnace. According to the embodiment presented here, the plant is particularly suitable for the treatment of fumes from a lime production furnace, the acid gases of which contain, in particular, sulfur oxides (SOx) and nitrogen oxides (ΝΟχ). . The installation 100 comprises a heat exchanger 1 of known type. The heat exchanger 1 is for example cooling tubes: the lower temperature fluid circulates inside the tubes, while the hotter fluid is in contact with the outer wall of the tubes. The heat exchanger 1 therefore comprises two fluid circulation circuits.
    A first flow circuit of the heat exchanger 1, for example the gas flow circuit in contact with the outer wall of the cooling tubes, is connected on the one hand to a duct 11 through which the fumes from the furnace arrive, and secondly to a desulphurization reactor 2, for example of the Venturi type, by an inlet conduit 25 of the reactor 2. The reactor 2 comprises an inlet formed by the succession, in the direction of circulation of the fumes , a convergent 5, a neck 4 and a divergent 3. The reactor 2 is fed with a sulfur oxide neutralization agent. Specifically, according to the example, the reactor 2 is supplied with fresh lime from a tank 28 which reacts with the sulfur oxides to form salts. The fresh lime is fed from the reservoir 28 to the neck 4 of the reactor 2 via a feed line 27. Optionally, as will be explained below, the reactor 2 is also fed with hydrated recycled lime. The humidity control in the reactor 2 is important. In fact, the moisture content must be sufficiently adjusted so that the lime behaves like a powdery reagent, and does not agglomerate into paste. In addition, the humidity must be controlled so that the evaporation of the water contained on the surface of the solid particles causes a controlled cooling of the fumes and promotes the absorption and the neutralization of the SO 2, and other possible acids (HCl and HF), while keeping the temperature of the fumes away from their dew point to avoid clogging problems. A maximum moisture content by weight of lime of 10% was determined to be adequate. The reactions in the reactor 2 are thus carried out for a short residence of the fumes in the reactor 2. The reaction residues are generally solid salts, such as calcium sulphate (CaSO 3) as residues of the sulfur oxide, but also calcium fluoride (CaF2) and calcium chloride (CaCl2). The installation 100 comprises a separation device 6, connected to the reactor 2 by a conduit 14 for filter inlet, and for separating the solid residues, in this case the formed salts and excess lime, gases. For this purpose, the separation device 6 comprises at least one bag filter composed of a plurality of filtration modules, through which the fumes pass, the solid residues, and possibly excess lime, being recovered and directed to a reservoir 9 recycling by a pipe 19 recovery. In addition, the particles which are deposited on the surface of the sleeves in the separation device 6 form a cake composed of still active hydrated lime particles forming an additional surface which makes it possible to continue the acid gas neutralization reaction within the device 6 separation and further increase the efficiency of the process. About 80-95% of the neutralization reaction takes place in the reactor, and the remainder occurs on the filter sleeves.
    As will be explained below, the sleeves are said to be catalytic because they comprise a catalyst for denitrification. For example, the sleeves are coated over their entire surface with a layer of a metal catalyst, which increases the contact area with the fumes. However, the catalyst can be placed inside the sleeves.
    The mixture in the recycling tank 9 is called recycled lime. The recycled lime is in solid form, making it easy to revalue. All or part of the recycled lime can be re-used in the desulphurization reactor 2. For this purpose, the recycled lime is taken by a supply duct 20 to a humidification drum 10, in which water, in a well controlled quantity, enters through a feed 22. The recycled lime is moistened, without exceeding maximum moisture content of 10% by weight of lime, is then sent to the desulfurization reactor 2 via a conduit 23 connected to the neck 4 of the reactor 2 to react again with the acidic pollutants in the fumes.
    Recirculation of lime recycled in reactor 2 maximizes the gas / solid contact, for better use of the reagent and less landfilling residues.
    Residues that are not recycled are dry, which makes it easier to landfill or even re-use as a soil application product. Thus, the main parameters to ensure a good S02 neutralization efficiency are in particular the stoichiometric excess of hydrated lime fed with respect to pollutants, the amount of recycled lime and its surface moisture which conditions the lowering of the flue gas temperature. , as well as the active surface (BET surface) of hydrated lime particles.
    The fumes at the outlet of the separation device 6 are then directed by a duct 16 to a ventilator 7. This allows in particular to overcome the pressure drop experienced in the filters of the separation device 6. Subsequently, the purified fumes are returned from the fan 7 to a chimney 8 by an outlet conduit 17.
    At least a portion of the fumes separated from the sulfur oxide residues arriving at the stack 8 is recirculated upstream of the process, to be cleaned of the nitrogen oxides by the so-called SCR method.
    More specifically, a portion of the flue gas in the chimney is returned to the exchanger 1, in the second flow circuit inside the cooling tubes. Thus the recirculated fumes, separated sulfur oxide residues, are heated by the fumes entering the first flow circuit, while the fumes entering the first circuit are cooled by the recirculated fumes. The energy consumption necessary to bring the fumes to the appropriate temperatures following the steps of their cleaning is thus reduced.
    The recirculated fumes exit the heat exchanger 1 through a contacting conduit 12, distinct from the inlet conduit of the reactor 2, and connected to a reservoir of a nitrogen oxide neutralization agent, for example ammonia. More precisely, the ammonia injector 26 is connected to the contacting conduit 12, so that ammonia mixes with the recirculated and heated fumes in the contacting conduit 12.
    The mixture of ammonia and recirculated fumes is combined with the gas / solid mixture leaving the Venturi reactor 2 via the junction of the contacting conduit 12 and the filter inlet conduit 14 connecting the reactor 2 to the separation device 6 at a point 15. combination. From the point of combination, the fumes in the filter inlet duct 14 are then a mixture comprising in particular: fumes having undergone a desulfurization process in the reactor 2 but not yet separated from the sulfur oxide residues ; fumes having undergone a desulfurization process in the reactor 2 and separated from the sulfur oxide residues; ammonia.
    The mixture then enters the separation device 6 with a compatible temperature for denitrification by the SCR method and comes into contact with the filter of the bag filter. The denitrification reactions reduce the nitrogen oxides and ammonia in the fumes to their ionic form to be transformed in particular into nitrogen gas and water vapor. The separation device 6 then also serves as a catalytic device for denitrification.
    The fumes are then directed as previously to the chimney 8, from where they are discharged into the atmosphere through an opening 18.
    The fumes thus removed have pollutants in very low concentration, respecting environmental regulations.
    One advantage of the process is that the residues recovered at the separation device 6, that is to say the salts (CaCl 2, CaF 2, CaSO 3), are dry, so the recovery of these residues in the market is possible.
    Another advantage is due to the minimal amount of water used to moisturize the hydrated lime; it is not necessary to perform a treatment of liquid effluents, which reduces the amount of equipment and possibly maintenance and operation costs.
    In addition, the arrangement of equipment in the process also has its advantages. For example, by placing the catalytic baghouses after the Venturi reactor 2, the majority of the SO 2 being removed in the reactor, the risks of poisoning the catalyst in the filters are significantly reduced.
    Another advantage provided by the filters is that catalyst particles can be deposited over the entire surface of their sleeve, which increases the reaction surface for denitrification. Thus, the nitrogen oxides are able to react over the entire length of the filter sleeves with the majority of the ammonia injected upstream of the filter, which prevents its leakage to the environment. Likewise, this filtration makes it possible to achieve a high efficiency in the separation of pollutants from the gases, since most of the constituents contained in the starting fumes can be removed.
    Finally, the process allows, within a single installation, to achieve desulfurization and denitrification of fumes, limiting energy consumption. Indeed, the method makes it possible to circulate the fumes from the furnace in two parallel circuits, namely a desulfurization circuit and a denitrification circuit, and to adjust the flue gas temperature in each circuit by minimizing the energy consumption.
    权利要求:
    Claims (9)
    [1" id="c-fr-0001]
    A method for treating flue gases from a combustion or calcination furnace comprising polluting species including sulfur oxides and nitrogen oxides, the process comprising the steps of: cooling the fumes at the exit of the furnace, setting in contact with the fumes with a sulfur oxide neutralization agent to obtain sulfur oxide residues, separation of the sulfur oxide residues and fumes, heating of at least a portion of the fumes separated from the oxide residues of sulfur, injecting a nitrogen oxide neutralizing agent into the heated fumes, contacting the fumes and the nitrogen oxide neutralizing agent with a catalyst to reduce the nitrogen oxides, the process characterized in that the cooling of the fumes at the outlet of the furnace is achieved by heating at least a portion of the fumes separated from the fume oxide residues. fre within the same heat exchanger (1).
    [2" id="c-fr-0002]
    The treatment method according to claim 1, wherein the fumes after the injection of the nitrogen oxide neutralizing agent are mixed with the fumes after contacting with the sulfur oxide neutralizing agent, the separation sulfur oxide residues and contacting with a catalyst being produced within a single separation device (6).
    [3" id="c-fr-0003]
    3. The treatment method according to claim 1 or claim 2, wherein the sulfur oxide neutralizing agent is lime.
    [4" id="c-fr-0004]
    4. Treatment process according to any one of the preceding claims, wherein during the contacting of the fumes with the sulfur oxide neutralization agent, the humidity in the flue gas is controlled.
    [5" id="c-fr-0005]
    5. The treatment method as claimed in claim 1, in which a part of the sulfur oxide residues is recycled as a sulfur oxide neutralization agent.
    [6" id="c-fr-0006]
    6. Flue gas treatment plant (100) for carrying out the process according to any one of the preceding claims, comprising a heat exchanger (1) connected to the furnace for cooling the smoke leaving the furnace, a reactor (2). desulfurization circuit connected to the heat exchanger (1) and in which the cooled fumes are brought into contact with the sulfur oxide neutralization agent, a device (6) for separating the sulfur oxide residues and fumes, an injector (26) of the nitrogen oxide neutralizing agent, and a catalytic device (6) for denitrification, the sulfur oxide residue separating device (6) being connected to the exchanger (1) of heat so that the fumes from the device (6) for separating the sulfur oxide residues are heated by the fumes leaving the furnace.
    [7" id="c-fr-0007]
    7. Installation (100) treatment according to the preceding claim wherein the device (6) for separating the sulfur oxide residues and the device (6) catalytic are combined into one and the same device (6) separation, the fumes after injecting the nitrogen oxide neutralizing agent being mixed in a filter inlet duct (14) of the installation (100) with the flue gases leaving the reactor (2).
    [8" id="c-fr-0008]
    8. Installation (100) treatment according to the preceding claim, wherein the device (6) of separation comprises at least one bag filter, a catalyst for denitrification being distributed on the surface of the filter sleeve.
    [9" id="c-fr-0009]
    9. Installation (100) treatment according to claim 7, wherein the separation device (6) comprises at least one bag filter, a catalyst for denitrification being placed inside the filter sleeve.
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    同族专利:
    公开号 | 公开日
    CA3003371A1|2017-06-15|
    EP3386610A1|2018-10-17|
    FR3044934B1|2021-08-06|
    US20180326351A1|2018-11-15|
    WO2017098105A1|2017-06-15|
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    法律状态:
    2016-11-21| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-16| PLSC| Publication of the preliminary search report|Effective date: 20170616 |
    2017-11-21| PLFP| Fee payment|Year of fee payment: 3 |
    2018-11-27| PLFP| Fee payment|Year of fee payment: 4 |
    2019-11-20| PLFP| Fee payment|Year of fee payment: 5 |
    2020-11-20| PLFP| Fee payment|Year of fee payment: 6 |
    2021-11-12| CA| Change of address|Effective date: 20211007 |
    2021-11-12| CD| Change of name or company name|Owner name: FIVES SOLIOS, FR Effective date: 20211007 Owner name: FIVES SOLIOS INC., CA Effective date: 20211007 |
    2021-11-12| CJ| Change in legal form|Effective date: 20211007 |
    2021-11-18| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562130A|FR3044934B1|2015-12-10|2015-12-10|PROCESS FOR TREATING FUMES FROM A COMBUSTION OR CALCINATION OVEN AND INSTALLATION FOR IMPLEMENTING SUCH A PROCESS|FR1562130A| FR3044934B1|2015-12-10|2015-12-10|PROCESS FOR TREATING FUMES FROM A COMBUSTION OR CALCINATION OVEN AND INSTALLATION FOR IMPLEMENTING SUCH A PROCESS|
    CA3003371A| CA3003371A1|2015-12-10|2016-11-22|Process for treating flue gases resulting from a combustion or calcination furnace and plant for the implementation of such a process|
    EP16813003.7A| EP3386610A1|2015-12-10|2016-11-22|Process for treating flue gases resulting from a combustion or calcination furnace and plant for the implementation of such a process|
    US15/774,601| US20180326351A1|2015-12-10|2016-11-22|Process for treating flue gases resulting from a combustion or calcination furnace and plant for the implementation of such a process|
    PCT/FR2016/053051| WO2017098105A1|2015-12-10|2016-11-22|Process for treating flue gases resulting from a combustion or calcination furnace and plant for the implementation of such a process|
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