EP0806467B1 - Procédé et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insaturés que les produits de départ, combinant une étape de vapocraquage et une étape de pyrolyse - Google Patents

Procédé et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insaturés que les produits de départ, combinant une étape de vapocraquage et une étape de pyrolyse Download PDF

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Publication number
EP0806467B1
EP0806467B1 EP97400998A EP97400998A EP0806467B1 EP 0806467 B1 EP0806467 B1 EP 0806467B1 EP 97400998 A EP97400998 A EP 97400998A EP 97400998 A EP97400998 A EP 97400998A EP 0806467 B1 EP0806467 B1 EP 0806467B1
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EP
European Patent Office
Prior art keywords
steam
zone
decoking
pyrolysis
steam cracking
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
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EP97400998A
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German (de)
English (en)
French (fr)
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EP0806467A1 (fr
Inventor
Christian Busson
Pierre Marache
Jean-Pierre Burzynski
Christian Dubois
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Engie SA
Original Assignee
IFP Energies Nouvelles IFPEN
Gaz de France SA
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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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

  • the invention relates to a process for pyrolysis of a hydrocarbon feedstock with at least two carbon atoms and simultaneously a process for decoking the coke deposited on the walls of the reactor.
  • pyrolysis reactors made of ceramic material have been used in which non-watertight partitions advantageously made of ceramic material determine channels where the charge and the reaction effluents circulate.
  • These partitions advantageously have a shape adapted to create turbulence and include, for example, cells or cavities in the level of heating means. These are usually ducts containing a heater electric or a gas burner.
  • Another drawback is related to the frequency of decoking of the tubes, every two or three month. Indeed, at the end of the cycle, the inside of the tubes is covered with a thick layer of coke. Coke may come off at times and is entrained by the gas flow to speeds of the order of 200 m / s risking damage to the ceramic sheaths of the pyrolysis oven downstream of the steam cracking oven.
  • An object of the invention is to provide a method for pyrolyzing a charge hydrocarbon without stopping the unit while allowing decoking of this unit.
  • Another object is to reduce the investment and operating costs of the unit.
  • Another object of the invention is to maintain the temperature of the installation substantially constant during its walk, to avoid thermal stresses which would not fail to occur, especially when using an oxygen-containing gas for the stage of decoking which implements an exothermic reaction while the pyrolysis step puts in performs an endothermic reaction.
  • the invention relates to a pyrolysis and decoking process in continuous in a reaction zone comprising a pyrolysis zone (40) made of material refractory, elongated in a direction (an axis) having a heating zone and a cooling zone following the heating zone, the heating zone comprising at least two rows (1, 2) substantially parallel to the axis, separated by a partition (70), advantageously not watertight, of refractory material between two rows successive, at least one of said rows (1) receiving hydrocarbons and steam of water, at least one other (2) of said rows essentially receiving water vapor, said rows comprising heating means (8) surrounded by sheaths (7) substantially parallel to each other and substantially perpendicular to the axis of the reactor, coke depositing in the reaction zone, the process being characterized in that a charge is circulated hydrocarbon containing at least one hydrocarbon with at least two carbon atoms to an adequate steam cracking temperature in a steam cracking zone containing at least at least two steam cracking tubes, at least two
  • the exit temperature from the steam cracking zone is generally lower than the outlet temperature of the zone heating zone pyrolysis.
  • the temperature in the steam cracking tube (s) where the steam cracking takes place the charge is advantageously maintained substantially equal to the temperature in the tubes where decoking takes place.
  • the temperature in the row or rows where the pyrolysis of the gas stream leaving the steam cracking zone is advantageously maintained approximately equal to the temperature in the row or rows where the decoking.
  • the outlet temperature of the heating zone relative to hydrocarbons and the exit temperature from the heating relative to the decoking effluent are about 1000 to 1400 ° C.
  • the amount of water vapor introduced into the zone of steam cracking, compared to that of the charge, in other words the steam weight ratio of water on charge, for a determined charge is greater than that corresponding to a conventional steam cracking of the same charge.
  • this ratio is greater than 0.5 while it is usually around 0.2.
  • the ratio is higher at 0.7 while it is usually around 0.5.
  • the ratio is greater than 1, for example equal to 2 whereas it is usually close to 1.
  • the choice of a high water vapor to charge ratio has the advantage of reducing the coke deposit. It will not be able to grow significantly since it is planned to decoker every four or five days for example, that is to say at a frequency corresponding to that of decoking the pyrolysis reactor, instead of decoking both at three months in the case of industrial steam crackers.
  • the steam cracker being connected to the pyrolysis furnace by a very short pipe, there is has practically no dead volume whereas when using the effluent from a steam cracker industrial as a pyrolysis reactor charge, having to cool the gas in a heat exchanger creates a large dead volume where secondary products are formed undesirable, by high temperature degradation of ethylene and acetylene.
  • the hydrocarbon supply in the tube is cut intended to be decoked and the flow of water introduced is substantially increased so as not to not cause excessive thermal disturbance in the gas preheating furnace upstream of the steam cracking zone.
  • the steam cracking furnace is usually heated by conventional gas burners, type radiant burners.
  • the load is generally preheated between 300 and 400 ° C.
  • the the temperature of the steam cracking zone is usually at most equal to 900 ° C.
  • the heating means of the pyrolysis reactor can be electrical resistances contained in sheaths as described in the above patents or they may be consisting of sheaths containing a gas burner as described in the patent application of the Applicant (FR 2715583).
  • Each row may include at least one layer of heating means surrounded by sheaths, substantially parallel to the axis of the reaction zone, these sheaths being substantially perpendicular to said axis.
  • heating elements either electric or comprising burners with gases, their number, the distance between them and their configuration are described in the patents cited above.
  • a cladding gas containing hydrogen and / or water vapor and / or carbon monoxide and / or an inert gas could be used and could also diffuse inside to outside of the sheaths without disturbing the pyrolysis reaction and without disturbing the decoking reaction.
  • the hydrocarbons collected and the decoking effluent can be mixed before being introduced into the cooling zone.
  • the hydrocarbons collected and the decoking effluent are cooled separately in their respective rows, located at the level of the cooling, then possibly mixed.
  • the cooling zone is usually a zone of direct quenching by a cooling, known to those skilled in the art, advantageously followed by a heat exchanger indirect contact generating steam (TLE: transfer line exchanger).
  • TLE transfer line exchanger
  • the installation has the advantage of being safe, reliable and easy to implement. She uses in the pyrolysis zone, refractory materials and more particularly materials ceramics known to those skilled in the art such as cordierite, mullite, silicon nitride or silicon carbide.
  • the invention also relates to a continuous pyrolysis and decoking unit for setting up work in particular of the process according to the invention, comprising a reactor (40) for pyrolysis of elongated shape in a direction (an axis) comprising at least two rows (1, 2) substantially parallel to the axis separated by a partition, (70) advantageously not sealed, of refractory material between two successive rows, each row comprising a plurality of heating means (8) arranged in at least one layer of heating elements surrounded by sheaths (7) of ceramic material substantially parallel to each other and substantially perpendicular to the axis of the reactor, at least one of the rows (1) being adapted to receive hydrocarbons and water vapor, at least one other (2) of said rows being adapted to receive water vapor, said pyrolysis reactor comprising heating control and modulation means connected to the heating means, the pyrolysis reactor further comprising means (47) for cooling the effluents products in each row, said unit being characterized in that it comprises a steam cracking reactor
  • Hydrocarbon supply lines 11, 12, 13, 14, 15, 16 controlled respectively by valves V1, V2, V3, V4, V5 and V6 introduce into a steam cracker 30 then into a reactor 40 for pyrolysis and decoking of hydrocarbons, for example ethane, from a line 10 mixed with water generally in vapor form provided by a line 60.
  • This line distributes it in lines 17, 18, 19, 20, 21 and 22 controlled respectively by valves V7, V8, V9, V10, V11 and V12.
  • valves V1 to V12 are adapted to allow the circulation of a mixture of hydrocarbons and water vapor in a certain number of tubes of the steam cracker 30 and of adjacent rows of the so-called pyrolysis reactor 40 and only of water vapor in other steam cracker 30 tubes and other adjacent rows of the so-called decoking reactor 40 for removing the coke which has been deposited during the steam cracking and pyrolysis reaction respectively.
  • Steam cracker tubes 31, 32, 33, 34, 35, 36 transporting the mixture of hydrocarbons and water or transporting water alone, connected respectively to lines 11 and 22, 12 and 21, 13 and 20, 14 and 19, 15 and 18 and finally, 16 and 17, are heated in the steam cracker 30 to a temperature of 850 to 900 ° C so as to crack part of the hydrocarbon charge and are connected respectively to rows 1, 2, 3, 4 , 5 and 6 of the pyrolysis reactor 40.
  • valve V1 closing the line 11
  • the tube 31 receives only the water vapor supplied by line 22 controlled by valve V12.
  • the tubes 32, 33, 34, 35 and 36 receive the hydrocarbon and water mixture, all the other valves mentioned being open.
  • All the tubes are preheated to around 400 ° C, essentially by convective heating in the first part of the heating oven, then at around 900 ° C in the second part of oven, essentially by radiative heating, by means of a plurality of burners.
  • the steam cracking effluent is introduced into the pyrolysis reactor 40 by lines of very short junction, not performing the function of quenching.
  • the pyrolysis reactor 40 adjacent to the steam cracking reactor 30 is divided into rows longitudinal (1, 2, 3, 4, 5 and 6) substantially parallel to its axis. These rows are separate from each other by partitions, 70, not leaktight in ceramic material, of shape comprising cells adapted to promote turbulence inside the row and therefore to favor the reaction. These rows contain sheaths of ceramic material 7 forming a sheet substantially parallel to the axis of the reactor. These sheaths are substantially parallel between them and substantially perpendicular to the axis of the reactor. They contain, for example, a plurality of electrical resistors 8 bathed in a sheath gas, chosen in the group formed by water vapor, hydrogen, carbon monoxide, an inert gas and a mixture of two or more of these gases.
  • the tube 31 containing water vapor is connected by a shortest heated line possible with row 1 of reactor 40.
  • the water vapor flow rate is increased inserted in the tube and in the row where decoking takes place, for example 2 to 3 times that used in the other tubes 32, 33, 34, 35 and the other rows 2, 3, 4, 5 and 6 where the pyrolysis.
  • the outlet temperature of the pyrolysis reactor 40 is heated to around 1200 ° C.
  • the terminal part of the various rows of reactor 40 intended for pyrolysis or for decoking, receives the pyrolysis or decoking effluents and each row is connected to a direct quenching line 47, comprising a controlled flow injector, for example of ethane if the charge is ethane, which allows these effluents to be cooled.
  • a direct quenching line 47 comprising a controlled flow injector, for example of ethane if the charge is ethane, which allows these effluents to be cooled.
  • lines 41, 42, 43, 44, 45 and 46 respectively connected to rows 1, 2, 3, 4, 5 and 6 mix the various effluents which are discharged through a line 50.
  • the effluents can be cooled by circulating through watertight conduits arranged in the end part of the rows by indirect quenching, then mixed as described above.
  • the pyrolysis and decoking effluents from rows 1, 2, 3, 4, 5 and 6 are collected by lines 41, 42, 43, 44, 45 and 46, then mixed and sent in a direct or indirect quenching zone and once cooled evacuated by line 50.
  • the heating elements 8 of the pyrolysis reactor are supplied with electrical energy from independently thanks to a pair of electrodes not shown in the figure, probes thermocouple pyrometry not shown are housed in the spaces where the charge and allow to automatically regulate the temperature of each section of heating, by a conventional regulation and modulation device not shown on the figure, depending on the temperature profile chosen which applies equally well to the reaction of pyrolysis than that of decoking the walls of the sheaths.
  • a temperature regulation device which may be the same, also makes it possible to control the temperature of the steam cracking reactor burners so that this temperature is lower than the outlet temperature of the oil collected and the final decoking effluent from the pyrolysis reactor.
  • a steam cracker-pyrolysis reactor assembly described according to FIG. 1 is used to crack a mixture of ethane and water vapor to produce a mixture of ethylene and acetylene.
  • the weight ratio of water vapor to ethane is 1.8.
  • the mixture (ethane-water) and the decoking vapor are brought to 900 ° C. in the reactor 30 steam cracking and heated in a substantially linear manner up to 1200 ° C in the pyrolysis reactor at an absolute pressure of 1.3 bar.
  • the steam cracker has six heating tubes.
  • the pyrolysis reactor has six heating rows substantially parallel to its axis and separated by partitions in the form of cells and ceramic material such as carbide silicon for example. Each row includes a tablecloth parallel to the axis of elements electric heaters.
  • the ducts perpendicular to the axis of the reactor, surrounding the electrical resistors are made of silicon carbide and contain a sheath gas which is nitrogen.
  • decoking is checked by disappearance of carbon monoxide, which is analyzed online by infrared, for example at the outlet of the pyrolysis oven. It is found that decoking is almost complete after 14 hours in each tube and row where it is carried out and we immediately go back into a steam cracking reaction situation for the tube which has been decoked and pyrolysis for the row which has been decoked.
  • An industrial steam cracker effluent is used as the pyrolysis hydrocarbon charge.
  • ethane having operated at a temperature of 900 ° C, this effluent being cooled by quenching indirect at 450 ° C.
  • This charge, introduced by line 10, is divided between five lines (n ° 11, 13, 14, 15 and 16) corresponding as for the example above to the five working rows in pyrolysis (n ° 1, 3, 4, 5 and 6).
  • each row of the pyrolysis zone 258 kg / h of hydrocarbons are introduced and of hydrogen and 86 kg / h of water from the conventional steam cracker and by each line 17, 18, 19, 20 or 22, 378 kg / h of water.
  • valve V2 of hydrocarbons In row 2 of the pyrolysis zone operating in decoking, the valve V2 of hydrocarbons being closed, 979 kg / h of water vapor is sent through valve V11 and line 21.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
EP97400998A 1996-05-06 1997-05-02 Procédé et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insaturés que les produits de départ, combinant une étape de vapocraquage et une étape de pyrolyse Expired - Lifetime EP0806467B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9605760 1996-05-06
FR9605760A FR2748273B1 (fr) 1996-05-06 1996-05-06 Procede et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insatures que les produits de depart, combinant une etape de vapocraquage et une etape de pyrolyse

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EP0806467A1 EP0806467A1 (fr) 1997-11-12
EP0806467B1 true EP0806467B1 (fr) 2000-12-27

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US (2) US5976352A (enExample)
EP (1) EP0806467B1 (enExample)
JP (1) JP4251303B2 (enExample)
AU (1) AU726569B2 (enExample)
CA (1) CA2204541C (enExample)
DE (1) DE69703763T2 (enExample)
ES (1) ES2154448T3 (enExample)
FR (1) FR2748273B1 (enExample)
ID (1) ID17841A (enExample)
MY (1) MY113653A (enExample)
NO (1) NO314507B1 (enExample)

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TWI434922B (zh) * 2007-08-23 2014-04-21 Shell Int Research 利用部份汽化作用及裂解線圈之個別控制組自烴進料產生低碳數烯烴之改良方法
US8278231B2 (en) * 2008-11-24 2012-10-02 Exxonmobil Chemical Patents Inc. Heat stable formed ceramic, apparatus and method of using the same
US8748686B2 (en) * 2008-11-25 2014-06-10 Exxonmobil Chemical Patents Inc. Conversion of co-fed methane and low hydrogen content hydrocarbon feedstocks to acetylene
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US8399372B2 (en) * 2009-05-18 2013-03-19 Exxonmobil Chemical Patents Inc. Stabilized ceramic composition, apparatus and methods of using the same
US8450552B2 (en) * 2009-05-18 2013-05-28 Exxonmobil Chemical Patents Inc. Pyrolysis reactor materials and methods
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JP5363932B2 (ja) * 2009-09-28 2013-12-11 株式会社日立製作所 化学装置
US8932534B2 (en) 2009-11-20 2015-01-13 Exxonmobil Chemical Patents Inc. Porous pyrolysis reactor materials and methods
US8784515B2 (en) 2010-10-14 2014-07-22 Precision Combustion, Inc. In-situ coke removal
CN107267168B (zh) * 2013-10-22 2020-05-15 贝克特尔碳氢技术解决方案股份有限公司 焦化炉出口的在线清管和散裂的系统
US10870803B2 (en) * 2016-07-16 2020-12-22 Ramin Karimzadeh Method for upgrading a hydrocarbon feed
US20190292466A1 (en) * 2018-03-26 2019-09-26 Dennis Carl England Control, method for pyrolysis process of low-rank-coal
CN112538365B (zh) * 2019-09-23 2022-11-01 中国石化工程建设有限公司 一种乙烯裂解炉裂解气管线清焦系统及裂解气管线防焦与除焦的方法
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CA2204541C (fr) 2008-07-15
DE69703763T2 (de) 2001-04-19
MY113653A (en) 2002-04-30
NO972070D0 (no) 1997-05-05
NO972070L (no) 1997-11-07
FR2748273B1 (fr) 1998-06-26
AU726569B2 (en) 2000-11-09
JP4251303B2 (ja) 2009-04-08
DE69703763D1 (de) 2001-02-01
NO314507B1 (no) 2003-03-31
AU2002997A (en) 1997-11-13
JPH10279507A (ja) 1998-10-20
ID17841A (id) 1998-01-29
US6322760B1 (en) 2001-11-27
FR2748273A1 (fr) 1997-11-07
EP0806467A1 (fr) 1997-11-12
ES2154448T3 (es) 2001-04-01
CA2204541A1 (fr) 1997-11-06
US5976352A (en) 1999-11-02

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