EP1497606B1 - Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur - Google Patents

Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur Download PDF

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Publication number
EP1497606B1
EP1497606B1 EP03709908A EP03709908A EP1497606B1 EP 1497606 B1 EP1497606 B1 EP 1497606B1 EP 03709908 A EP03709908 A EP 03709908A EP 03709908 A EP03709908 A EP 03709908A EP 1497606 B1 EP1497606 B1 EP 1497606B1
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Prior art keywords
exchanger
approx
temperature
oxidation
oxidizing fluid
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German (de)
English (en)
French (fr)
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EP1497606A1 (fr
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Willy Nastoll
Dominique Sabin
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IFP Energies Nouvelles IFPEN
Alfa Laval Packinox SAS
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IFP Energies Nouvelles IFPEN
Packinox SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
    • F28G13/00—Appliances or processes not covered by groups F28G1/00 - F28G11/00; Combinations of appliances or processes covered by groups F28G1/00 - F28G11/00

Definitions

  • the invention relates to a process for at least partial elimination of carbonaceous deposits inside a heat exchanger.
  • Many processes in the petroleum refining and petrochemical industry use indirect heat exchangers between two fluids, particularly process fluids, to achieve thermal recovery and reduce energy consumption.
  • charge / effluent exchangers are used by which the charge of a chemical reactor is heated, at least in part, by the effluent of this reactor.
  • exchangers operating in the installations for the implementation of these various processes sometimes contain various impurities or various heavy products which can cause fouling, in particular carbon fouling such as coke,
  • These deposits do not correspond to well-identified compounds of constant composition and morphology but to products of considerable variability as regards both the chemical composition, especially the H / C ratio, and the morphology, the possible presence of heteroatoms, for example sulfur, nitrogen or metals, for example the presence of iron in sometimes large amounts, may in some cases reach several percent or even 10, or 20% weight or more.
  • Oven coils are typically made of strong tubes of high thickness (usually between 5 and 15 mm) and typically have a free end, being suspended by springs or counterweights, or resting on supports allowing expansion. They are therefore insensitive to differential expansions due to temperature heterogeneities. Moreover, their life is limited, for example frequently between 3 and 8 years in steam cracking furnaces which are subject to the most frequent decoking.
  • the exchange surfaces typically have smaller thicknesses (typically less than 3 mm and even of the order of 1 mm or less for plate heat exchangers used in refineries).
  • their mechanical realization leads to much more welds (for example at the tubular plates for the tubular exchangers, or all around the plates for plate heat exchangers).
  • exchangers are basically mechanically more constrained systems than furnace tubes, much more sensitive to differential expansions or "hot spots", and therefore much more fragile from a thermomechanical point of view.
  • expected lifetime of an exchanger reaches and usually exceeds 20 years, which excludes any procedure that can lead to premature aging of the device.
  • the conventional method used for the decoking of exchangers is to perform mechanical decoking, by ringarage exchange tubes, or by the mechanical action of a jet of water to very strong pressure of several tens of megapascals (hydraulic decoking).
  • These conventional techniques are, however, more restrictive in terms of service life and maintenance than the technique of decoking the furnaces by combustion, because of the obligation to cool the equipment and perform disassembly to access the tubes to be decoked.
  • these techniques are not applicable to welded plate heat exchangers: These heat exchangers can not be decoked mechanically or hydraulically due to a gap between plates, which is often much smaller than 10 mm, and the existence of corrugations on the plates. preventing the passage of a cleaning tool or the access of a hydraulic jet.
  • the French patent FR 2,490,317 describes quenching exchangers for steam cracking effluents which make it possible to carry out combustion decoking.
  • the decoking procedure described essentially consists in draining the apparatus at a moderate temperature (preferably at 550 ° C or less) and then raising the temperature to decoker (i.e., as indicated, until about 750 to 600 ° C and preferably up to about 700 ° C).
  • This procedure is described exclusively for very specific exchangers of the tubular type with double tubes, which also use special mechanical design provisions and a particular thermal device (thermal insulation body placed around a group of double tubes), allowing reduce the fragility of the device during decoking.
  • oxidants such as, for example, ozone or hydrogen peroxide.
  • the invention provides a method for the controlled oxidation removal at a low temperature of a substantial part or all of the carbonaceous deposits of the exchangers of a certain type of process, by controlled oxidation in situ, with current technical means, and without risk of mechanical damage to the device.
  • the process does not require the modification of exchangers and is applicable to all types of exchangers tubular and also to welded plate heat exchangers.
  • the invention also proposes a process for at least partial elimination of carbonaceous deposits in a relatively fast manner, which makes it possible to limit the duration of the intervention, always without any risk of mechanical deterioration of the apparatus.
  • the invention is very generally applicable to heat exchangers whose operating temperature is less than about 540 ° C, and preferably less than about 520 ° C. Preferably, it is not used in high temperature services, for example for the decoking of quench heat exchangers for steam cracking, for reasons which will be explained below.
  • the conventional temperature of a deposit oxidation step is by definition the maximum temperature of a heat exchange wall at the hot end.
  • This temperature which may be fixed or variable, will according to the invention conventionally calculated at the beginning of the exchange zone, after the dispensing zone and / or fluid discharge. This calculation can be carried out easily by those skilled in the art using the general laws of thermal. However, there may be minor differences in the calculation result depending on the calculation method used. Those skilled in the art will then be able to realize the invention to consider the highest value which corresponds to a conservative value for the implementation of the invention.
  • Removal of in-situ deposits means that the exchanger remains in place during the deposition removal operation, and is not disassembled and transported to another site.
  • hydrotreating installation comprising a device for removing deposits
  • this installation comprises at least the main technical means of the device installed on the site of the installation, and which can be easily connected (for example by a hose, a pipe sleeve etc ...) in case of occurrence of fouling of the exchanger.
  • the method according to the invention achieves an in situ removal of these deposits, that is to say without moving the exchanger which remains installed on its site of use.
  • the method according to the invention can however also be implemented on another site.
  • the temperatures of the fluids supplying or coming from the exchanger are kept below about 500 ° C. throughout the duration of the oxidation treatment, and the hot approach of the exchanger remains below about 100 ° C. during the entire duration of the oxidation treatment.
  • Controlled oxidation of deposits formed in hydrotreatment exchangers has been carried out, most often with operating temperatures between about 200 and about 450 ° C. These deposits have been surprisingly sensitive to low temperature oxidation, including low oxygen levels such as 1 to 2.5% and even less. These deposits could be oxidized and reduced or eliminated without the need to grind to increase the contact surface with the oxidizing fluid. It has also been found that it is possible to control mild oxidation conditions and to avoid any excursions of temperatures and hot spots during the oxidation procedure.
  • deposits formed at relatively low temperature and which have not matured at high temperatures, about 520 to 540 ° C due to the operating conditions of the exchanger are different in nature from a coke formed or calcined at relatively high temperature, and are much more easily oxidized.
  • Preferred applications according to the invention are the removal of deposits in service temperature exchangers less than or equal to about 450 ° C.
  • thermomechanical modeling To validate the absence of deterioration of an exchanger including a plate heat exchanger in the field of hot approaches up to 100 or even 120 ° C.
  • the oxygen content of the oxidizing fluid during the oxidation treatment is less than or equal to about 2.5 mol%, and preferably less than or equal to about 2.0 mol%.
  • a range of oxygen levels particularly well suited is the range of 0.4 to 2.0 mol%. The preferred range depends on several factors. One of them is the nature of the inert fluid composing the main part of the oxidizing fluid:
  • the oxygen content of the oxidizing fluid during the oxidation treatment is such that the temperature difference in adiabatic total combustion is less than about 120 ° C and very preferably less than 100 ° C.
  • the differential temperature of the adiabatic total combustion of an oxidizing fluid is defined as the temperature increase obtained in adiabatic total combustion (the oxygen being in the form of CO2 and H2O), starting conventionally with 450 ° C, at the average pressure of the operation, and with methane in stoichiometric quantity as reagent of oxygen.
  • the method according to the invention can be implemented according to several variants.
  • the oxidation treatment comprises at least two controlled oxidation steps in which the first of these two stages circulates in the exchanger a first oxidizing fluid of oxygen content c1 between about 0.4 and about 1.5 mol% at a temperature between about 420 and about 490 ° C for a period of at least four hours and sufficient to oxidize at least a portion of the carbonaceous deposits, then circulated in the exchanger during the second of these two steps a second oxidizing fluid of oxygen content c2 greater than c1 and between about 1.3 and about 2.0 mol% for a period of at least two hours at a temperature between about 420 and about 490 ° C.
  • the oxidation treatment is started with very moderate oxidation conditions, which makes it possible to eliminate deposits that are very easy to oxidize under very mild conditions.
  • the oxidation is then continued to obtain a complementary elimination of deposits with a slightly higher oxygen content.
  • This variant makes it possible to further increase the control of the temperatures and the hot approach of the exchanger to moderate values.
  • the oxidation treatment comprises at least one main controlled oxidation stage and a complementary controlled oxidation stage, in which a principal oxidizing fluid is circulated in the exchanger during the main stage.
  • c3 oxygen content of between 0.8 and 2.0 mol% at a temperature of between about 420 and about 480 ° C for a period of at least four hours and sufficient to oxidize most of the carbonaceous deposits, and then circulating in the exchanger during the complementary step a complementary oxidizing fluid of oxygen content c4 strictly less than c3 and between about 0.2 and about 0.8 mol%, for a period of at least two hours at a temperature of from about 480 to about 525 ° C.
  • the elimination of most of the deposits is carried out in a main controlled oxidation step, and a controlled oxidation-controlled operation is carried out at a relatively higher temperature but with a very low oxygen content. . This makes it possible to continue some removal of deposits without risk of thermal runaway or to reach too high temperatures.
  • oxidation can be started by a first controlled oxidation step in which a first oxygen-content oxidizing fluid is circulated in the exchanger.
  • c1 of from about 0.4 to about 1.5 mol% at a temperature between about 420 and about 490 ° C for a period of at least four hours and preferably at least 12 hours, and sufficient to oxidize at least part of the carbonaceous deposits (for example with approximately 450 ° C and 1% oxygen)
  • a second stage with a second oxidizing fluid of oxygen content c2 greater than c1 and between about 1.3 and about 2 0 mol% for a period of at least two hours, and preferably at least 8 hours, at a temperature of between about 420 and about 490 ° C (for example with 450 ° C and 2% oxygen)
  • the process is more particularly suited to carbonaceous deposits in service temperature exchangers not exceeding about 520 ° C to 540 ° C, which provide more readily oxidizable carbonaceous deposits.
  • the circulation in the exchanger can be carried out with the same fluid or different fluids in the two passes, in parallel or in series, and can be carried out at upward or downward co-current (for a vertically arranged exchanger) or against current.
  • At least a portion of the flow of oxidizing fluid is circulated in the two passes of the exchanger in series and co-current.
  • At least a portion of the flow of oxidizing fluid is circulated during the controlled oxidation step in the two passes of the exchanger in series, with an intermediate cooling by mixing or heat exchange with a colder fluid. This ensures better temperature control.
  • the oxidizing fluid (s) consist for the most part either of water vapor or of nitrogen, with the addition of a minor amount of air and possible minor amounts of carbon monoxide or carbon dioxide. If nitrogen is used as inert, mainly in closed circuit, the oxidizing fluid can indeed also include CO2.
  • the CO2 can be removed in the recycle loop by absorption (for example by washing with amines).
  • the loop gas may optionally also include small amounts of carbon monoxide CO.
  • the operating pressure (maximum pressure in the exchanger) during the oxidation process can vary within wide limits, for example between 0.01 and 10 MPa.
  • the preferred pressure range is between 0.1 and 2 MPa, and more particularly between 0.1 and 1 MPa.
  • the exchanger is preheated to a temperature of at least about 360 ° C., and preferably at least about 400 ° C. in the absence of air. and oxygen before starting the oxidation treatment. This makes it possible to start the oxidation treatment with a notable temperature and to reduce the duration of the oxidation treatment. This can be very variable depending on the nature and quantity of deposits. It can be between 4 hours and about 400 hours or more, the preferred duration is between 6 and 200 hours, and very preferably between 8 and 150 hours. Most often, an oxidation treatment of at least 24 hours duration will be used.
  • the exchanger is preferably preheated initially under an essentially nitrogen atmosphere, at a temperature of at least about 160 ° C. and sufficient to substantially prevent any subsequent condensation of water.
  • water before supplying the exchanger with a fluid consisting mainly of water vapor, for the final preheating and / or the oxidation treatment. It is indeed preferable to avoid condensation of water which can cause corrosion in the presence of certain impurities, for example chlorides.
  • the exchanger is preferably cooled in an atmosphere consisting essentially of water vapor to a temperature of less than 400 ° C. but greater than about 160 ° C.
  • the exchanger is fed with a fluid consisting essentially of nitrogen, to achieve a final cooling of the exchanger below 100 ° C without risk of condensation of water in the exchanger.
  • the exchanger can not be cooled below a temperature for which there is a risk of condensation of water and proceed immediately to reactivate the exchanger without significant cooling. However, this is only possible when the temperatures of all the fluids entering and leaving the exchanger are sufficiently high.
  • the process according to the invention is applicable in particular to exchangers of the welded metal plate type disposed inside a metal ferrule. It is then preferably possible to circulate, in a space between the plates and the shell, during the preheating and / or the controlled oxidation step, at least a portion of at least one of the fluids supplying or coming from the exchanger. This tends to reduce temperature differences between the plates and the ferrule.
  • this space can be placed under a nitrogen atmosphere, for example at a pressure equal to or slightly greater than the highest pressure of the exchanger.
  • the exchanger may also be of the tubular, tube, tube (s) and calender type.
  • the process is carried out in a device for at least partial elimination of carbonaceous deposits by controlled oxidation in situ in a heat exchanger operating at most 540 ° C., preferably at most 520 ° C., in a treatment plant.
  • hydrocarbon said device comprising means for supplying an oxidizing fluid essentially comprising an inert gas of the group formed by water vapor, nitrogen, and mixtures thereof, and a quantity of oxygen less than 2.5 mol%, and at least one means for maintaining the temperatures of the fluids supplying or coming from the exchanger during the oxidation treatment below about 500 ° C.
  • the device also preferably comprises at least one means for maintaining the hot approach of the exchanger, during the oxidation treatment, below about 100 ° C., for example one of the technical means previously mentioned for process variants: means for reducing the supply temperature of at least one of the fluids, means for reducing the oxygen content, means for measuring the maximum temperature of all the fluids entering or leaving the exchanger with high alarm, means of measurement of the hot approach with high alarm, etc.
  • the device comprises at least one means for supplying an oxidizing fluid essentially comprising an inert gas of the group formed by water vapor, nitrogen, and mixtures thereof, as well as an amount of oxygen less than 2.5 mol% (this means being for example a connection pipe to an air or oxygen network), at least one means for adjusting the oxygen content (for example control valve and flow meter ) and at least one means for reducing this content (eg automated control system for reducing or closing the air control valve, or operating instructions manual for the operator) connected (in the case of an automated procedure) to an indication or an alarm of high temperature of one of the fluids supplying or coming from the exchanger, or an indication or an alarm (high) of average temperature of the hot side of the exchanger or a indication or alarm of value too much the warm approach of the exchanger.
  • an oxidizing fluid essentially comprising an inert gas of the group formed by water vapor, nitrogen, and mixtures thereof, as well as an amount of oxygen less than 2.5 mol%
  • this means being for example a connection pipe to
  • the oxidation procedure can be managed by a programmable controller or a process control computer.
  • the distillable hydrocarbon hydrotreatment plant comprising a charge / effluent heat exchanger operating at at most 540 ° C, preferably at most 520 ° C, and also comprising a device for at least partial elimination of carbonaceous deposits in the controlled oxidation exchanger in situ in this heat exchanger, this device comprising means for supplying an oxidizing fluid essentially comprising an inert gas of the group formed by water vapor nitrogen, and mixtures thereof, and an amount of oxygen less than 2.5 mol%, and at least one means for maintaining the temperatures of the fluids supplying or coming from the exchanger during the oxidation treatment below about 500 ° C.
  • the hydrotreatment plant comprises a device also comprising at least one means for maintaining the hot approach of the exchanger below about 100 ° C.
  • the aforementioned means relating to the hydrotreatment plant may comprise, for example, in the event of a hot approach that is too high and / or a temperature that is too high, of one of the fluids supplying or coming from the exchanger, a valve that makes it possible to reduce the oxygen content of the oxidizing fluid and / or a system for reducing the preheating of at least one of the fluids supplying the exchanger.
  • the hydrotreatment plant comprises a reactor comprising at least one hydrotreatment catalyst, and comprises a device for at least partial elimination of carbonaceous deposits, this device comprising at least one common means , on the one hand, the at least partial removal of carbonaceous deposits in the exchanger, and on the other hand, and partly at least simultaneously, the regeneration of the catalyst by controlled oxidation.
  • This means may be for example an at least partly common circulation loop (for example a nitrogen-rich gas recycling fan or compressor, a common means of analysis of the controlled oxidation effluent composition).
  • the deposition removal installation preferably uses common means with the hydrotreatment plant (for example, for example, the process furnace for preheating the oxidizing fluid, flow measurements, or temperature measurements with alarms. high temperature, pipes etc ).
  • the hydrotreatment plant for example, for example, the process furnace for preheating the oxidizing fluid, flow measurements, or temperature measurements with alarms. high temperature, pipes etc .
  • hydrotreatment plants concerned mention may be made, in particular, of the hydrotreatment plants of naphtha (before catalytic reforming), hydrotreatment of gasoline, in particular catalytic cracking, to desulphurize this gasoline for example at 10 ppm by weight or even less, hydrotreatment of middle distillates or cuts diesel fuel (diesel fuel bases) for desulphurization at 10 ppm weight or less, or domestic fuel oil, or kerosene, and vacuum distillate hydrotreatments for desulfurization and / or partial dearomatization.
  • gasoline in particular catalytic cracking
  • middle distillates or cuts diesel fuel (diesel fuel bases) for desulphurization at 10 ppm weight or less
  • domestic fuel oil, or kerosene or vacuum distillate hydrotreatments for desulfurization and / or partial dearomatization.
  • the hydrotreatment plant comprises a device, comprising at least one common means, for on the one hand the at least partial elimination of carbonaceous deposits in the exchanger, and on the other hand partly, and in part at least simultaneously, regeneration of the catalyst by controlled oxidation.
  • the figure 1 represents an alternative device for at least partial elimination of deposits, with recycling of a part of the oxidizing fluid after oxidation of the deposits.
  • the recycling is especially, and especially at the beginning of the deposit removal procedure a recycling of inert, the oxygen can be consumed significantly or completely.
  • This plant preferably operates with an inert gas comprising mainly nitrogen, with minor amounts of monoxide or carbon dioxide from recycling.
  • Exchanger 1 of the figure 1 is a charge / effluent exchanger for example a diesel hydrotreating facility (during its normal service), and is of the plate type comprising a welded plate bundle 3, disposed inside a shell 2 resistant to pressure.
  • the two passes of the exchanger (one, 4, for the circulation of the effluent, the other, 5, for that of the load during normal service are represented symbolically in broken line.
  • the device comprises the furnace 19 for preheating the oxidizing fluid, which is also the process furnace of the hydrotreatment plant.On the outlet of the furnace 19, the oxidizing fluid (which can level possibly being substantially composed of inert) flows in the line 20.
  • Part of this fluid can optionally be derived by the line 21 to a regeneration circuit (including decoking) of the catalyst contained in the hydrotreatment reactor 27; this regeneration being preferably carried out at least partly simultaneously with the removal of deposits in the exchanger.
  • the fluid derived by the line 21 is joined by an air supply arriving via the line 22, to carry out a decoking of the catalyst contained in the reactor 27.
  • the oxygen content is measured by the analyzer 23 disposed on the line 21.
  • the fluid then passes through the exchanger 24 to adjust its temperature (by cooling or reheating) to the desired value for the regeneration of the catalyst, this catalyst regeneration temperature may be different from that used for the removal of deposits in the exchanger .
  • a temperature sensor 26 with a high temperature alarm is installed on the fluid outlet line 25 of the exchanger 24.
  • the fluid (oxidant) for decoking the catalyst then joins the reactor 27, then downstream of the reactor joined the line 20 by the line 28, downstream end of the branch.
  • the gaseous effluent from these two lines circulates in the downstream part of the line 20 which comprises a temperature tap 29.
  • the line 20 is joined by an air supply via the line 30 on which is installed a controlled control valve 31 to adjust the oxygen content of the oxidizing fluid used for oxidation of the exchanger deposits.
  • this oxidizing fluid can optionally be taken from the line 32, pass through the free space between the plate bundle 3 and the shell 2 (to homogenize their temperatures) and be evacuated via the line 33 which joins the line 6 mentioned below.
  • the main oxidizing fluid after optional sampling via the line 32, circulates in the terminal portion of the line 20 on which is disposed an analyzer 34 for measuring the oxygen content of the oxidizing fluid in order to allow control of this content, and a temperature measurement 42 for measuring the temperature of the oxidizing fluid supplying the pass 6 (effluent side) of the exchanger 1.
  • the oxidizing fluid whose oxygen content is preferably adjusted to the desired value, then joins the exchanger it passes through the pass 4 (effluent side of the hydrotreatment).
  • the oxidizing fluid exits the exchanger and flows in the line 6.
  • this line 6 comprises a temperature measurement 40 (with high temperature alarm), is joined by line 33 mentioned above, then is joined by a line 35 for supplying relatively cold fluid.
  • This power supply optional but preferred, allows to cool the oxidizing fluid, which has generally warmed by crossing a first time the exchanger in the pass 4, before feeding the pass 5 fouled by deposits.
  • the relatively cold fluid supplied by line 35 can be, for example, nitrogen, water vapor or a part of the oxidant (or substantially inert) fluid recycled by example recycled from line 18 upstream of the preheating furnace 19 (this recycling line is not represented on the figure 1 ).
  • the process control takes account of this arrival of cold fluid for the evaluation of the oxygen content of the oxidizing fluid.
  • the oxidizing fluid thus cooled then circulates in the downstream part of the line 6, which comprises a temperature measurement 43, then feeds the fouled passage of the exchanger, in order to carry out the controlled oxidation of the carbonaceous deposits, preferably vertically ascending , having co-flowed with the circulation in the passage 4.
  • the oxidizing fluid (possibly become substantially inert) circulates in the line 7, which comprises a temperature measurement 41 with high alarm and an analyzer 8 (or several analysis apparatus) which measures the CO, CO2, and residual oxygen contents of the oxidation effluent of the deposits.
  • This oxidation effluent is then cooled in the heat exchanger 9, then flows in the line 10 and supplies a gas treatment plant 11.
  • This installation preferably comprises a separating flask for removing the condensed water, and optionally a CO2 removal system, for example by washing with amines.
  • the residual gas flows in the line 12, and is recompressed in the compressor (or fan) 13.
  • part of the residual gas flowing in the line 14 is purged by the line 15, to eliminate a surplus of gas resulting in particular from the nitrogen of the air supplied by the lines 22 and 30.
  • the complementary part comprising mainly nitrogen and minor amounts of CO2 and CO, is recycled by the line 16.
  • This line 16 is joined by a nitrogen supply line 17, used mainly for the start-up and cooling phases of the installation in which the fluid supplying the exchanger is below about 160 ° C. and could condense in the exchanger, which could cause corrosion. Line 16 then feeds the heat exchanger (optional) 9, then joins oven 19 via line 18.
  • This device of the figure 1 therefore preferably operates with a recycling loop mainly comprising nitrogen. It makes it possible to be able to adjust separately, on the one hand for the controlled oxidation of the carbon deposits of the exchanger, and on the other hand (optionally) for the decoking of the catalyst, the parameters of the oxidation operation, and in particular the oxygen content and the (or the) feed temperature (s) of the oxidizing fluid.
  • the parameters of the oxidation operation and in particular the oxygen content and the (or the) feed temperature (s) of the oxidizing fluid.
  • the (heated) fluid from pass 4 is cooled by mixing with recycled gas taken from line 18 (in a non-controlled manner). shown) and fed by line 35, to reduce the inlet temperature of the fouled passage 5, measured by the temperature taken 43, to a value of 430 ° C. It is controlled that the temperatures measured by the 40,41,42,43 taps are all below 500 ° C and that the hot and cold approaches are less than 100 ° C. If one of these parameters exceeds the desired value, the oxygen content and also preferably the temperature at the temperature setting 42 are reduced by limiting the preheating in the oven 19.
  • a device for at least partial elimination of deposits can be implemented in a different way from that of the figure 1 .
  • the fluids can circulate in co-current downward and non-co-upflow, and / or supply first pass 5 then in series the pass 4 (unlike the figure 1 ), or against the current with the pass 4 fed first, or the pass 5 fed first, either upward or downward.
  • the installation may also include other equipment or technical means not shown such as filters or pressure measurements, various regulations etc ... well known in the field of processes or chemical engineering.
  • the device of the figure 2 represents an alternative device for at least partial elimination of deposits, without recycling a part of the oxidizing fluid after oxidation of the deposits.
  • the oxidizing fluid mainly comprises steam with a small amount of air.
  • the oxidizing fluid circulates in series against the current in the heat exchanger, first in the pass 4 (in downflow), flows in the lines 53 and 54, then in the fouled pass 5 (load side) in the updraft , then exits through line 55 and is evacuated (to the flare, to the chimney or in a final combustion zone, these elements not being represented).
  • the steam is supplied by the line 50, with a flow rate measured by the flow meter 60.
  • the air is added via the line 51, with a flow rate measured by the flow meter 61.
  • the temperature and the oxygen content of the preheated fluid which flows in the line 52, respectively by the temperature tap 45 and the analyzer 34.
  • the installation also comprises other temperature taps 44, 46 and 47, with high alarms, and a cooling of the fluid leaving the exchanger, via the line 53, by means of a relatively cold fluid (for example unheated steam) fed by the line 35, optional but preferred.
  • the fluid from the mixture is reintroduced into the bottom of the exchanger to feed the pass 5 (load side) and allow the oxidation of deposits.
  • Example 1 According to the Invention: Tests on a Model:
  • a stainless steel welded plate heat exchanger model comprising two chevron corrugated welded plates arranged in an outer shell heated by electrical resistances. The plates are surrounded by nitrogen and heated both by radiation from the outer shell and by convective exchange with nitrogen.
  • the initial pressure drop of the model under nitrogen is measured under precisely measured flow conditions.
  • the charge is preheated to 200 ° C, its temperature is measured in the model, from 200 to 250 ° C, and then the evolution of the pressure drop is observed: It does not change, indicating that the coking or fouling does not occur.
  • Air is then gradually supplied starting from an oxygen content of 0.5% by volume, up to 1.5% by volume. It is ensured that the outlet temperature of the model does not exceed 470 ° C (this value may be higher than the regulated temperature due to the combustion of the deposits), reducing if necessary the supply temperature of the model (below 430 ° C or lower) and oxygen content (below 1% volume or lower).
  • the amount of carbon monoxide CO and carbon dioxide CO2 is measured in the effluents of exit. After a period of 10 hours, it is found that the amount of CO + CO2 becomes unmeasurable, and the controlled oxidation is stopped, then the model is cooled, and the pressure drop of the model is measured. under the same conditions as those of the uncovered model. The measured pressure drop is only 2.4% higher than the initial pressure drop, which indicates that the model is very slightly dirty or possibly not at all fouled due to the accuracy of the measurements. It is noted after dismantling that the welded plates of the model are not distorted at all, that no coloration of the metal reflecting the occurrence of a hot spot is observed and that the mechanical and metallurgical state of these plates is identical to the initial state.
  • the load is preheated to 310 ° C, its temperature is raised in the model, from 310 to 348 ° C, then the evolution of the pressure drop is observed: It does not change, indicating that, as in the previous case, coking or fouling does not occur.
  • Example 1 The charge is then modified by addition of a small amount of heavy pollutants and traces of oxygen, as indicated in Example 1.
  • the pressure drop increases, although more slowly than in Example 1.
  • the pressure drop under nitrogen is only 1.2% higher than that of the clean apparatus, a value that is not significant given the accuracy of the measurements. This indicates that the model is very slightly fouled or not at all fouled. It is also noted, after dismantling, that the welded plates of the model are not at all deformed, that no coloration of the metal reflecting the occurrence of a hot spot is observed and that the mechanical and metallurgical state of these plates is identical to the initial state. The plates are then cut at the periphery (destructive test) to observe the appearance of the internal surfaces. This is normal, without metallurgical degradation or surface condition. No trace of carbonaceous deposit is found, indicating that the oxidation of the deposits was substantially complete.
  • the controlled oxidation of the apparatus is preferably carried out without waiting for the fouling to be very high.
  • the treatment can be carried out if the pressure loss increases unexpectedly, or has increased rapidly or progressively about 50% of the normal value, and preferably as soon as the pressure drop has increased by about 15 to 40%. It is then preferable to carry out the oxidation treatment without waiting for an additional increase, and / or a chemical transformation of the deposits by maturation, which can make cleaning longer or more difficult.
  • the process according to the invention makes it possible to achieve an in situ elimination of carbonaceous deposits in exchangers operating at moderate or medium temperatures, in particular in desulfurization and hydrotreatment plants, and this in an efficient, fast and reliable manner, unlike the methods known from the prior art.
  • the combination of different usable technical means are techniques very well mastered in refinery or on-site petrochemical, which makes the process easy to implement.
  • the invention also opens up new opportunities for the use of plate heat exchangers with a more effective and / or easier to remove deposition process than the methods of the prior art.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
EP03709908A 2002-03-15 2003-01-30 Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur Expired - Lifetime EP1497606B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0203209 2002-03-15
FR0203209A FR2837273B1 (fr) 2002-03-15 2002-03-15 Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur
PCT/FR2003/000280 WO2003078914A1 (fr) 2002-03-15 2003-01-30 Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur

Publications (2)

Publication Number Publication Date
EP1497606A1 EP1497606A1 (fr) 2005-01-19
EP1497606B1 true EP1497606B1 (fr) 2010-01-06

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US (1) US6929015B2 (zh)
EP (1) EP1497606B1 (zh)
JP (1) JP4730683B2 (zh)
CN (1) CN100458355C (zh)
AT (1) ATE454602T1 (zh)
AU (1) AU2003214340A1 (zh)
CA (1) CA2478598C (zh)
DE (1) DE60330854D1 (zh)
ES (1) ES2337243T3 (zh)
FR (1) FR2837273B1 (zh)
RU (1) RU2303049C2 (zh)
WO (1) WO2003078914A1 (zh)

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* Cited by examiner, † Cited by third party
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FR2837273B1 (fr) * 2002-03-15 2004-10-22 Inst Francais Du Petrole Procede d'elimination au moins partielle de depots carbones dans un echangeur de chaleur
CN100425940C (zh) * 2005-10-21 2008-10-15 中国石油化工股份有限公司 一种大型管壳类换热设备管束的高温裂解除垢设备及除垢方法
DE102007006647A1 (de) * 2007-02-06 2008-08-07 Basf Se Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts
JP5713592B2 (ja) * 2009-08-27 2015-05-07 三菱重工環境・化学エンジニアリング株式会社 熱分解付着物除去方法及び熱分解ガス化システム
RU2482413C2 (ru) * 2011-06-29 2013-05-20 Государственное образовательное учреждение высшего профессионального образования Казанский государственный технический университет им. А.Н. Туполева (КГТУ-КАИ) Способ предотвращения образования и роста углеродистых отложений на стенках теплообменных каналов
RU2489760C1 (ru) * 2012-02-29 2013-08-10 Открытое акционерное общество "Свердловский научно-исследовательский институт химического машиностроения" (ОАО "СвердНИИхиммаш") Способ удаления осадка мох-топлива с катода электролизера
KR101364179B1 (ko) * 2013-05-31 2014-02-18 (주)썬켐 화학플랜트용 열교환기 클리닝 방법 및 장치
CN103757650B (zh) * 2013-10-25 2015-10-07 沈阳黎明航空发动机(集团)有限责任公司 一种超声波除积碳方法
WO2017111035A1 (ja) 2015-12-25 2017-06-29 日本化薬株式会社 ブタジエン製造用触媒の再生方法

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Also Published As

Publication number Publication date
CA2478598C (fr) 2011-03-01
RU2004130478A (ru) 2005-04-10
JP4730683B2 (ja) 2011-07-20
CN100458355C (zh) 2009-02-04
RU2303049C2 (ru) 2007-07-20
US20030230324A1 (en) 2003-12-18
CN1643330A (zh) 2005-07-20
FR2837273B1 (fr) 2004-10-22
FR2837273A1 (fr) 2003-09-19
JP2005521021A (ja) 2005-07-14
EP1497606A1 (fr) 2005-01-19
ATE454602T1 (de) 2010-01-15
DE60330854D1 (de) 2010-02-25
ES2337243T3 (es) 2010-04-22
CA2478598A1 (fr) 2003-09-25
WO2003078914A1 (fr) 2003-09-25
AU2003214340A1 (en) 2003-09-29
US6929015B2 (en) 2005-08-16

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