EP3186338B1 - Process for decoking a hydrocarbon steam cracking furnace - Google Patents

Process for decoking a hydrocarbon steam cracking furnace Download PDF

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Publication number
EP3186338B1
EP3186338B1 EP15753278.9A EP15753278A EP3186338B1 EP 3186338 B1 EP3186338 B1 EP 3186338B1 EP 15753278 A EP15753278 A EP 15753278A EP 3186338 B1 EP3186338 B1 EP 3186338B1
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EP
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Prior art keywords
quench
steam
effluent
oil
decoking
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EP15753278.9A
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German (de)
English (en)
French (fr)
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EP3186338A1 (en
Inventor
David B. Spicer
Subramanian Annamalai
James M. Frye
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/802—Diluents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam

Definitions

  • the present invention relates to the field of thermal cracking hydrocarbons for the production of olefins, particularly low molecular weight olefins such as ethylene. More particularly the invention relates to methods for removal of coke deposits that form during such thermal cracking processes.
  • Steam cracking also referred to as pyrolysis, is used to crack various hydrocarbon feedstocks into olefins, preferably light olefins such as ethylene, propylene, and butenes.
  • Conventional steam cracking utilizes a pyrolysis furnace that has a firebox and radiant coil section, among other features.
  • the hydrocarbon feedstock typically enters the furnace as a liquid (except for light feedstocks which enter as a vapor) wherein it is heated and at least partially vaporized by indirect contact with hot flue gas and by direct contact with steam.
  • the vaporized feedstock and steam mixture is then introduced into the radiant coil section where the pyrolysis cracking chemistry primarily takes place.
  • the resulting products comprising olefins leave the radiant coils and are quenched to halt further pyrolysis reactions.
  • a direct oil quench connection is often required downstream of the primary TLE.
  • the oil quench connection allows addition of quench oil into the pyrolysis product stream to provide heat transfer from the product stream directly to the injected quench oil.
  • Oil quench fittings have been designed as a specialized technology for the addition of oil into the furnace effluent in a manner that does not cause rapid plugging.
  • a process is desired for removing coke from a steam cracking furnace having a transfer line exchanger and oil quench connection that reduces or prevents stratified flow, provides improved decoking effluent temperature control and reduces mechanical fatigue of piping downstream of the oil quench fitting.
  • a decoking process utilizing steam (“quench steam”) rather than liquid water injection for cooling the effluent from the process reduces or prevents stratified flow, provides improved decoking effluent temperature control and reduces mechanical fatigue of piping downstream of the oil quench fitting.
  • Quench steam avoids stratified flow and provides tighter control of the decoking process effluent temperature. Tighter control allows the target effluent temperature to be optimized and set closer to the upper metallurgical temperature limit of the downstream piping. This provides a cost saving optimization by avoiding over quenching of the process effluent that can be realized, for example, in reduced quench steam demand.
  • non-stratified (vapor phase only) flow that is substantially free of liquid water is advantageous, for example, when the decoking effluent is directed into the furnace firebox.
  • any liquid water entering the firebox would instantly vaporize with a corresponding rapid increase in volume that could damage the firebox insulation system. Utilizing quench steam instead of quench water avoids this problem.
  • One feature of the invention is a decoking process for removing coke formed during steam cracking of a hydrocarbon feed in a furnace having a firebox, radiant coils, a transfer line exchanger, and an oil quench connection wherein liquid quench oil is injected to directly cool the steam-cracked hydrocarbon.
  • the process comprises several steps. First, the flow of hydrocarbon feed to the furnace and flow of quench oil to the oil quench connection is stopped. Second, a decoking feed comprising steam and air is supplied to the furnace under conditions sufficient to at least partially combust coke accumulated on the interior of the radiant coils, the transfer line exchanger, and the quench connection. Third, quench steam is supplied and injected into the decoking process effluent in an amount sufficient to cool the decoking process effluent below the metallurgical temperature limit of downstream piping.
  • a pyrolysis furnace suitable for carrying out the inventive decoking process.
  • the pyrolysis furnace comprises a number of elements.
  • a hydrocarbon feed conduit and a dilution steam conduit in fluid communication with the hydrocarbon feed conduit is described.
  • the dilution steam conduit facilitates mixture of the dilution steam and the hydrocarbon feed.
  • a radiant coil in fluid communication with the combined steam and hydrocarbon feed is also provided.
  • a firebox heats the exterior of the radiant coil to provide a cracked hydrocarbon effluent from the radiant coil.
  • a transfer line exchanger in fluid communication with the radiant coil is described to provide indirect heat transfer for cooling the hydrocarbon effluent.
  • an oil quench connection in fluid communication with the transfer line exchanger is described to provide direct heat transfer by injection of quench oil into the hydrocarbon effluent.
  • a quench steam connection in fluid communication with the oil quench connection is included for injecting quench steam during decoking.
  • Feedstocks that may be employed herein may be any feedstock adapted for cracking insofar as they may be cracked into various olefins, and may contain heavy fractions such as high-boiling fractions and evaporation residuum fractions.
  • a pyrolysis furnace 1 includes a radiant firebox 103, a convection section 104 and flue gas exhaust 105.
  • Fuel gas is provided via conduit 100 and control valve 101 to radiant burners 102 that provide radiant heat to a hydrocarbon feed to produce the desired pyrolysis products by thermal cracking of the feed.
  • the burners generate hot gas that flows upward through the convection section 104 and then out of the furnace to atmosphere via the flue gas exhaust 105.
  • Hydrocarbon feed is conducted via conduit 10 and control valve 12 to a preheating conduit 13 in convection section 104 where the feed is preheated by indirect contact with hot flue gas.
  • a plurality of feed conduits 11 are arranged in parallel. Although not shown, each of the plurality of feed conduits 11 may be provided with a control valve 12. Each of the plurality of conduits 11 is in fluid communication with a corresponding preheating conduit (not shown) in parallel to preheating conduit 13 in convection section 104.
  • the use of the term "plurality of conduits" is meant to refer to the fact that the convection section 104 is arranged wherein each multiple preheating conduit bank has at least two conduits in parallel. Four conduits are represented in FIG. 1 , although furnaces having 3, 4, 6, 8, 10, 12, 16, 18 parallel conduits are known.
  • the preheated hydrocarbon feed is mixed with dilution steam.
  • Dilution steam is provided via conduit 20 through control valve 22 to steam preheating conduit 23 in convection section 104 where the dilution steam is preheated by indirect contact with hot flue gas. Dilution steam is added to provide the amount of H2O required to achieve the desired hydrocarbon partial pressure during pyrolysis reaction.
  • a plurality of steam conduits 21 may be provided corresponding to the plurality of feed conduits 11.
  • the mixture of dilution steam and preheated hydrocarbon feed is conducted via conduit 25 to heat exchange conduit 30 in convection section 104.
  • the dilution steam and preheated hydrocarbon feed mixture can be conducted to a vapor liquid separator (not shown) to remove non-volatile hydrocarbon components that promote coking when cracked.
  • a plurality of heat exchange conduits may be provided.
  • the heated mixture Upon exiting the heat exchange conduit 30, the heated mixture is passed to radiant coil 40 in radiant section 103 for thermal cracking of the hydrocarbon.
  • a plurality of radiant coils may be provided.
  • the temperature of the heated mixture exiting conduit 30 is generally designed to be at or near the point where significant thermal cracking commences.
  • the temperature of the thermally cracked hydrocarbon exiting the radiant coil 40 can vary from about 790°C (1450°F) for some very heavy gas oil feeds to about 900°C (1650°F) for ethane or propane feeds.
  • the furnace effluent is rapidly cooled.
  • the furnace effluent is conducted to one or a series of more than one indirect transfer line heat exchanger(s) (TLE) 50 where the heat energy from the furnace effluent is indirectly transferred to heat water provided via conduit 51 to produce high pressure steam conducted away via conduit 52.
  • TLE indirect transfer line heat exchanger
  • a direct oil quench connection is often required downstream of the TLE.
  • the oil quench connection allows addition of quench oil into the furnace effluent stream to provide heat transfer from the furnace effluent directly to the injected quench oil.
  • the furnace effluent is cooled primarily by the vaporization of the quench oil.
  • Oil quench fittings have been designed as a specialized technology for the addition of oil into the furnace effluent in a manner that does not cause rapid plugging.
  • Non-limiting examples of oil quench fitting designs may be found in U.S. Pat. Nos. 8,177,200 ; 3,593,968 ; 6,626,424 ; 3,907,661 ; 4,444,697 ; 3,959,420 ; 5,061,408 ; and 3,758,081 .
  • the quench oil may be injected through spray nozzles in the quench fitting.
  • the quench oil is added in a manner to form a continuous liquid film on a cylindrical wall of the quench fitting.
  • Still other examples add the quench oil through a single port in the quench fitting.
  • Yet another example adds oil through a grooved circumferential slot in the quench fitting so as to create liquid film along the wall of the fitting.
  • Another non-limiting example adds oil through a porous jacket into the furnace effluent stream.
  • the partially cooled furnace effluent leaving TLE 50 is conducted via conduit 53 to direct oil quench fitting 60.
  • Quench oil preferably a distillate oil and more preferably an aromatic-containing distillate oil
  • a plurality of quench oil conduits 71 may be provided.
  • Preferred liquid quench fluids 70 that may be particularly useful may include a liquid quench oil, such as an aromatic oil.
  • Preferred aromatic oil may have a final boiling point of at least about 400°C (750°F).
  • Other particularly useful liquid quench fluid may include an aromatic distillate, such as a distillate that is recovered from cooled furnace effluent stream 90.
  • Sufficient quench oil 70 is combined with partially cooled furnace effluent 53 in direct quench fitting 60 to ensure the temperature of the cooled furnace effluent 90 is appropriate for feeding downstream separation equipment, for example, a primary fractionator (not shown) that receives furnace effluent at about 288°C (550°F) to 315°C (600°F).
  • a plurality of direct quench fitting effluent conduits 91 may be provided.
  • the conventional method of removing coke from the radiant coils of a cracking furnace is decoking.
  • the hydrocarbon feed 10 is interrupted to the furnace and steam 20 continues passing through the furnace.
  • the furnace effluent 90 is redirected away from the recovery section of the olefins plant (not shown) to atmosphere.
  • Air is added via conduit 10 to the steam passing through the furnace to create a decoking feed air/steam mixture 25.
  • the air/steam mixture is heated in radiant coils 40 to remove at least a portion of the coke deposits by controlled combustion.
  • the effluent from radiant coils 40 is cooled in transfer line exchanger 50 and in quench fitting 60.
  • the decoking process effluent is ultimately exhausted to atmosphere, it is conventional to substitute water in place of the quench oil for injection at the quench fitting 60.
  • the flow of quench oil in conduit 70 is halted via valve 72 at the beginning of the decoking process.
  • Water is introduced via conduit 80 and valve 82 and injected into quench fitting 60.
  • a plurality of water conduits 81 may be provided.
  • the cooled effluent 90 is then exhausted to the atmosphere, either via a decoke drum, e.g., a cyclonic separator (not shown), or via the furnace firebox 103 and flue gas exhaust 105.
  • the large temperature difference between the vapor and liquid streams in the piping makes control of the quench water addition rates to maintain a stable temperature difficult since a temperature sensor in the pipe is contacted by the hot vapor or relatively cold liquid stream.
  • the partially combusted coke vapor effluent 90 must be cooled sufficiently below metal temperature limits of the downstream piping, e.g., less than 450°C (840°F) for carbon steel. Because of the variation in measured temperature, it is customary to design the water quench control system to operate with a temperature setpoint comfortably below the metal temperature limits, e.g., 315°C (600°F) - 340°C (645°F) for carbon steel. Even so, the rapid cycling of measured temperature leads to rapid cycling of quench water addition rate, further increasing the thermal fatigue of the piping.
  • the invention described herein does not use the conventional decoking process. More particularly, the invention utilizes steam rather than water injection for cooling the effluent from the process. Utilizing steam instead of liquid water reduces or prevents stratified flow, provides improved decoking effluent temperature control and reduces mechanical fatigue of piping downstream of the oil quench fitting.
  • FIG. 2 where like numerals indicate like parts to those described in FIG. 1 , the hydrocarbon feed 10 is interrupted to the furnace and steam 20 continues passing through the furnace. The furnace effluent 90 is redirected away from the recovery section of the olefins plant (not shown) to atmosphere. Air is added via conduit 10 to the steam passing through the furnace to create a decoking feed air/steam mixture in conduit 25.
  • the air/steam mixture is heated in radiant coils 40 to remove at least a portion of the coke deposits by controlled combustion.
  • the effluent from radiant coils 40 is cooled in transfer line exchanger 50 and in quench fitting 60.
  • the flow of quench oil in conduit 70 is halted via valve 72.
  • steam (“quench steam”) is injected to cool the decoking process effluent 90.
  • Quench steam may be injected downstream of the quench fitting as indicated in FIG. 2 via conduit 110, valve 111 and conduit 112, or quench steam may be injected into the quench fitting via conduit 80, or quench steam may be divided between the two injection points.
  • the rate of steam injection via conduit 110 or conduit 80 is controlled to achieve desired process effluent temperature in conduit 90.
  • the quench steam does not produce stratified flow, it does not suffer from variations in measured temperature.
  • the result is tighter control of the decoking process effluent temperature. Tighter control allows the target effluent temperature to be optimized and set closer to the upper metallurgical temperature limit of the downstream piping.
  • the decoking process effluent temperature may be controlled ⁇ 30°C below the upper metallurgical temperature limit of the downstream piping. This provides a cost saving optimization by avoiding over quenching of the process effluent that can be realized, for example, in reduced quench steam demand.
  • non-stratified (vapor phase only) flow that is substantially free of liquid water is especially well-suited, for example, when the decoking effluent is directed into the furnace firebox (connection not shown). In such applications, any liquid water entering the firebox would instantly vaporize with a corresponding rapid increase in volume that could damage the firebox insulation system.
  • the amount of quench steam required to cool the decoking process effluent may be further reduced by adding liquid water to desuperheat the quench steam supply.
  • the liquid water added to the quench steam absorbs heat lowering the temperature of the quench steam and the liquid water undergoes a phase change from liquid water into additional quench steam.
  • FIG.3 where like numerals indicate like parts to those described in FIG. 1 and FIG. 2 , illustrates one potential embodiment of this option.
  • Sufficient liquid water is injected via conduit 120 and valve 121 in order to substantially desuperheat the quench steam in conduit 112.
  • the quench steam may be desuperheated to about 3.5°C, 5°C, 7°C, 10°C, 15°C, or 25°C, above the quench steam saturation temperature.
  • the quench steam provided via conduit 80 may be desuperheated.
  • another advantage of desuperheating the quench steam is reduced velocity in the piping and corresponding reduced erosion rates from suspended coke particulates.
  • Heavy gas-oil may be fed via conduit 10 at a rate of 91 Mg/hr (200 klb/hr).
  • Quench oil may be provided via conduit 70 at a rate of 182 Mg/hr (400 klb/hr) to cool the furnace effluent.
  • the temperature in effluent conduit 53 can reach 580°C (1075°F).
  • the equipment downstream of conduit 90 (not shown) may be made of carbon-steel and is designed to operate at temperatures below 449°C (840°F).
  • Quench water may be injected via conduit 80 to cool the decoking effluent.
  • the target effluent temperature is 315°C (600°F) achieved by a quench water flow rate of about 14 Mg/hr (31 klb/hr).
  • the quench oil fitting 60 in this example is designed for 182 Mg/hr (400 klb/hr) of quench oil flow, poor distribution results when only 14 Mg/hr (31 klb/hr) of quench water is injected into the quench oil fitting. As previously described, the maldistribution leads to stratification, mechanical fatigue, and variable temperature control.
  • Example 1 The same 91 Mg/hr (200 klb/hr) heavy gas oil feed used in Example 1 may be fed to a similar furnace configured as illustrated in FIG. 2 .
  • the quench fitting 60 is designed for 182 Mg/hr (400 klb/hr) flow of quench oil.
  • quench steam may be supplied via conduit 80 or via conduit 110 or via both conduit 80 and conduit 110 to cool the decoking process effluent.
  • the target effluent temperature may be raised to 427°C (800°F) (closer to the carbon-steel temperature limits of 449°C (840°F)) and may be achieved using about 40 Mg/hr (88 klb/hr) of medium pressure 188°C (370°F) quench steam.
  • Using quench steam avoids the problems of stratification, mechanical fatigue, and variable temperature control by eliminating the use of quench water.
  • the same 91 Mg/hr (200 klb/hr) heavy gas oil feed used in Example 1 may be fed to a similar furnace configured as illustrated in FIG. 3 .
  • the quench fitting 60 is designed for 182 Mg/hr (400 klb/hr) flow of quench oil.
  • quench steam may be supplied via conduit 110 to cool the decoking process effluent.
  • quench steam that is close to its saturation temperature may be used.
  • conduit 90 Since the operating pressure of conduit 90 may be about 0.82 atm gauge (12 psig) or less, the quench steam may be cooled to 121°C (250°F) (about 3.5°C above the quench steam saturation temperature) with no risk of adding excess water to the decoking effluent.
  • the decoking effluent may be cooled to the same 427°C (800°F) in conduit 90 as in Example 2 using about 34 Mg/hr (75 klb/hr) of desuperheated steam made up of about 1.3 Mg/hr (3 klb/hr) of desuperheating water (supplied via conduit 120) and about 32.7 Mg/hr (72 klb/hr) of 188°C (370°F) medium pressure steam (supplied via conduit 110). Less quench steam is required than was required in Example 2 which reduces volumetric flow rate and velocity in the piping, also reducing erosion rates.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP15753278.9A 2014-08-28 2015-08-07 Process for decoking a hydrocarbon steam cracking furnace Active EP3186338B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201462042920P 2014-08-28 2014-08-28
EP14191533 2014-11-03
US201462092623P 2014-12-16 2014-12-16
PCT/US2015/044328 WO2016032730A1 (en) 2014-08-28 2015-08-07 Process and apparatus for decoking a hydrocarbon steam cracking furnace

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EP3186338A1 EP3186338A1 (en) 2017-07-05
EP3186338B1 true EP3186338B1 (en) 2018-09-26

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EP (1) EP3186338B1 (zh)
CN (1) CN106661461B (zh)
SG (1) SG11201610863YA (zh)
WO (1) WO2016032730A1 (zh)

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TW202338071A (zh) * 2022-03-22 2023-10-01 美商魯瑪斯科技有限責任公司 供烯烴生產用的電熱蒸汽裂解爐

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SG11201610863YA (en) 2017-01-27

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