WO2005111175A1 - Procede de craquage thermique d'hydrocarbures - Google Patents

Procede de craquage thermique d'hydrocarbures Download PDF

Info

Publication number
WO2005111175A1
WO2005111175A1 PCT/IN2004/000135 IN2004000135W WO2005111175A1 WO 2005111175 A1 WO2005111175 A1 WO 2005111175A1 IN 2004000135 W IN2004000135 W IN 2004000135W WO 2005111175 A1 WO2005111175 A1 WO 2005111175A1
Authority
WO
WIPO (PCT)
Prior art keywords
coke
sulfur
feed
additive
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.)
Ceased
Application number
PCT/IN2004/000135
Other languages
English (en)
Inventor
Kumar Kisor Chaudhuri
Garimella Padmavathi
Marayil Ravindranathan
Jayant V. Kelkar
Nagarathinam Shenbaga Murthy
Atul G. Kathiria
Yatendra K. Lodha
Devpal Rana
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.)
Indian Petrochemicals Corp Ltd
Reliance Industries Ltd
Original Assignee
Indian Petrochemicals Corp Ltd
Reliance Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Indian Petrochemicals Corp Ltd, Reliance Industries Ltd filed Critical Indian Petrochemicals Corp Ltd
Priority to PCT/IN2004/000135 priority Critical patent/WO2005111175A1/fr
Publication of WO2005111175A1 publication Critical patent/WO2005111175A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/22—Non-catalytic cracking in the presence of hydrogen
    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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

Definitions

  • the present invention relates to the process for the thermal cracking of hydrocarbons. More particularly, the present invention relates to a method of inhibiting coke formation on surface of the cracking coils. It also relates to anti coking additives that are useful in inhibiting coke formation on such cracking coil surfaces and related equipment.
  • Thermal cracking of hydrocarbon feedstocks in presence of steam is the most important commercial process for the production of light olefins like ethylene, propylene, butanes and butadienes and aromatics, the main feedstocks of the petrochemical industry. Jhe hydrocarbon feed stocks range from ethane to vacuum gas oils and any combination thereof.
  • the operation is generally carried out in gas fired furnaces containing long vertical coils or tubes in parallel.
  • the number of coils in the furnace is a function of the ethylene capacity per furnace.
  • the hydrocarbon is diluted with stream to minimize undesired side reactions and is preheated up to the required transition temperature for pyrolysis in the radiation section. This temperature is known as cross over temperature.
  • the cross over temperature is in the range of 600-650 °C.
  • the stream to hydrocarbon ratio by weight is from 0.3 to 0.5 depending on the feedstock. Cracking takes place in radiation section. In radiation section high heat fluxes can be achieved.
  • the process gas temperature at the coil outlet is around 820-840 °C.
  • the coil inlet pressure is in the range of 1.5 to 2 kg/ cm2g.
  • the residence time is in the range of 0.4 to 0.66 s.
  • the effluent from the furnace is rapidly quenched by transfer line exchanger (TLE) in which high pressure steam is produced.
  • TLE transfer line exchanger
  • the rapid quench reduces loss of olefins by minimizing secondary reactions.
  • the effluent from TLE is fractionated into its constituents or groups of them. Thermal cracking of hydrocarbon liquids and gases is always accompanied by formation of coke.
  • the coke is deposited on the coil surface and metal surfaces of the processing equipment.
  • the coke on coil surface hampers the heat transfer from the furnace to the reacting gas.
  • the external tube skin temperature has to be increased without exceeding the limits imposed by metallurgy.
  • the reduction in coil diameter due to the coke layer increases the coil pressure drop.
  • U.S. Patent No. 5,463,159 describes a method of treating ethylene furnaces with hydrogen sulfide to reduce coke and/or coke formation.
  • U.S. Patents No. 5,565,087 and 5,616,236 disclose method sfor inhibiting coke and carbon monoxide formation by treating the cracker tubes with sulfur compounds in the presence of hydrogen
  • U.S. Patent No. 5,954,943 discloses a method of reducing coke deposition in cracking furnaces with a combination of sulfur and phosphorus containing compounds.
  • U.S. Patent No. 4,666,583 discloses a method of reducing coke on coil by contacting the metal with an additive selected from the group of gallium and tin and a metal with an additive selected from the group of gallium and tin and a combination of gallium and antimony.
  • U.S. Patent No. 4,962,264 discloses a method of reducing coke by adding rare earth elements or compounds such as cerium and lanthanum elements or compounds to the hydrocarbon feed.
  • 5,000,836 discloses that coke can be inhibited by adding a combination of molybdenum and boron to hydrocarbon feed.
  • U.S. Patent No. 5,128,023 discloses that a combination of boron compound and a dihydroxybenzene added to hydrocarbon feed reduces coke formation and deposition.
  • U.S. Patent No. 5,358,626 discloses a method of controlling coke by adding a mixture of Group 1 A metal salt, a Group IIA metal salt and a boron acid or salt thereof to the hydrocarbon feed stock.
  • Various phosphorous based additives such as phosphoric acid (U.S. Patent No. 3,531,394), phosphate and phosphite mono and diesters (U.S. Patent No.
  • the present invention provides a method for inhibiting coke formation and deposition of coke on metal surfaces of a pyrolysis furnace which is used for thermal cracking of hydrocarbons.
  • the method comprises of adding a 100-300 ppmw amount of sulfur oil which is a mixture of organic disulfides in the carbon number range of C 2 -C 4 , to the hydrocarbon feed and subjecting the feed to cracking temperatures in the range of 820-855 °C.
  • the additive is a low value product from petroleum refinery finding useful application in coke inhibition.
  • organic disulfides comprise alkyl disulfides, wherein the preferred alkyl radicals are methyl and ethyl and the typical sulfur content in sulfur oil is 60%
  • the additive is as effective as commercial sulfur additives and the sulfur concentration in the feed is most preferably between 140 and 150 ppmw.
  • the sulfur content in gas and liquid products is within allowable limits.
  • the additive is decomposable at reaction conditions and completely converted in the furnace.
  • the metal surface is a cracker coil wall, said metal being iron or nickel or both.
  • the feed is any hydrocarbon or their mixtures that can be cracked for olefins production.
  • the coil is specially designed for coke profile measurement without breaking the coil Detailed description
  • the present invention relates to a process for thermal cracking of hydrocarbons. More particularly, the present invention relates to a method of inhibiting coke formation on surface of the cracking coils. It also relates to anti coking additives that are useful in inhibiting coke formation on such cracking coil surfaces and related equipment.
  • a process for thermal cracking of hydrocarbons which comprises feeding said hydrocarbon feed to a pyrolysis furnace, and subjecting it to hydrocracking characterized in that from 100-300 ppmw of sulfur oil which is a mixture of organic disulfides in the carbon number range of C 2 -C j is added to said hydrocarbon feed and said feed is subjected to cracking at a temperature in the range of 820-855 °C.
  • the present invention also relates to a method for inhibiting coke formation on the surface and/or coils of a pyrolysis furnace during a hydrocracking process, which comprises adding to the hydrocarbon feed stock, from 100-300 ppmw of sulfur oil which is a mixture of organic disulfides in the carbon number range of C 2 -C 4 ⁇ and subjecting said feed to cracking at a temperature in the range of 820-855 °C.
  • sulfur oil which is a mixture of organic disulfides in the carbon number range of C 2 -C 4 ⁇ and subjecting said feed to cracking at a temperature in the range of 820-855 °C.
  • Sulfur oil is produced from LPG Mercaptan oxidation (merox) units of refining complex as a byproduct when mercapatan laden LPG is treated with sodium hydroxide for mercaptans removal.
  • Boiling range °C 110-180
  • FIG. 1 is a schematic representation of the naphtha cracker pilot plant
  • FIG. 2 is a typical temperature profile
  • FIG. 3 is coke profile of the coil in the hyrdocracking furnace
  • FIG. 4 is comparison of coke profiles of blank runs with additives
  • FIG. 5 is relative reduction of coke rate with respect to blank run
  • FIG. 6 is spalling rate of bland run and runs with additives
  • coke is not deposited uniformly even under isothermal operation, but rather according to a profile.
  • FIG. 1 represents the schematic representation of the naphtha cracker pilot plant with a coil, the design of which is very novel in which the present invention has been carried out.
  • Naphtha and water are stored in two SS tanks, 10, 12 at atmospheric pressure.
  • the tanks are provided with level gauges using which the flow rate of the feeds can be' checked regularly.
  • the tanks are placed on electronic weighing balances 14, 16 of 50 kg. capacity each. The amount of feed consumed in the particular run is given by these balances.
  • metering pumps 18, 20 of 20 1/h capacity each for the pumping of the feeds.
  • the suction is taken from the storage tanks through spiral tube to minimize pulsations in the feed flow.
  • vaporizers naphtha vaporizer 22 and water vaporizer 24 made of SS316.
  • the heat is supplied by electrically heated furnaces to vaporize the naphtha and water.
  • the outlets of vaporizers are sent to a mixer 26 where the temperature is raised to around 200 to 250 °C.
  • the mixer outlet flows through three electrically heated super heaters 28, 30,32 and enters the top of the furnace reactor tube inlet 34 at 600 °C which is taken as cross over temperature.
  • the coil 36 is 'w type' with a provision to measure temperature and coke profiles.
  • the coke samplers (3.4x1.2 cm) made of same material as the coil can be inserted at the top and bottom location of each pass of the coil.
  • the reactor tube is 5.30m long, made of Incoloy 800H, and has an internal diameter of 26.7 mm.
  • the coil is suspended in an electrically heated furnace with three zones 388, 40 and 42.
  • the furnace is 1.856m long and 0.5842m wide and 1.174 m high.
  • Each zone temperature can be independently controlled to set to any desired temperature profile in the coil.
  • Sixteen thermocouples are located in the reactor coil to measure process gas temperature profile. The external wall temperature is measured at 12 locations. Thermocouples are located in the air space between the heating element and tube, along the outer surface of the coil and in the process flow stream.
  • the furnace exit gases are quenched to around 600 °C.
  • the naphtha feed flow rate can be varied up to 10 kg/h.
  • the gases are further cooled in two heat changers 44, 46 in series to condense the stream and heavier fractions in the gas mixture.
  • the condensed water and liquid are then collected and weighed for mass balance calculations. Non condensed gases were further cooled and measured by a wet gas meter 48.
  • a small portion of furnace outlet stream is passed through Fluid Data.
  • Sample conditioner 50 and the gas from the top of the conditioner is sent for online analysis by two GCs 52, 54.
  • the output of the GCs is sent to PC 56 for area intergration and processing.
  • the pilot plant is connected with DARWIN system, which controls the process parameters and has several on-line functions like data acquisition and data treatment.
  • the cracked gas samples is simultaneously analysed on two gas chromatographic
  • GC thermal conductivity detector
  • HP 3362 Hydrogen and methane are detected by a thermal conductivity detector (TCD) in the first system (HP 3362). The analysis takes about 5 minutes. All the hydrocarbons except hydrogen are detected by a flame ionization detector on second system (HP 5890) and this analysis takes around 60 minutes. Peak identification and integration is performed by a commercial integration packages. With these, the product distribution in terms of weight percentage can be determined. Since the feed flow rate is known, yields of products % wt/wt of HC feed and material balance can be calculated. Test procedure For a typical run the furnace is turned on and the temperature is slowly increased while air is fed in continuously. After desired temperature profile is established, water is introduced in to the unit. After few minutes, air is discontinued and naphtha is fed into the unit.
  • TCD thermal conductivity detector
  • the flow rates of naphtha and water are set in such a way that the desire dilution ratio is maintained.
  • the temperature of the furnace is dropped, as soon as naphtha is introduced into the reactor due to the endothermic reactions.
  • the temperature is increased slowly to reach to the desired temperature profile and coil outlet temperature in 20 to 30 minutes.
  • the product gases are analysed by using two gas chromatographs. Typical material balance is performed for an hour period by taking the weights of naphtha and water, the amount of liquid product collected, total amount of gas measured through gas flow meter during the one hour period and product gas analysed.
  • run the product gas is analysed once in four hours. After completion of a run, the reactor is cooled and coke samplers are weighed to obtain surface coke. The spalled coke collected in the dead leg is measured. The reactor is then steam-air decoked.
  • Coke profile The knowledge of coke profile and coking rate of a coil is essential for evaluating various anti coking additives. Series of accelerated coking experiment have been carried out in this unit to obtain coke profile in the coil during thermal cracking of naphtha. The amount of coke deposited is calculated from the weight gain of the coke samplers after run for 12 hours. The coke samplers are removed for weighting after cooling before decoking. The rate of coking is expressed as weight of coke per unit surface area of the sampler per unit time. Knowing the ratio of surface areas of coke sampler and coil walls, the total coke yield can be calculated.
  • EXAMPLE -1 A run was carried out at severity of 840 °C COT and 0.5 stream dilution ratio for 12 hours with naphtha feed of 38-140 °C cut consisted of 76.79% paraffins, 17.33% naphthenes and 5.88%o aromatics by weight. Reproducibility of the run was tested by repeating the experiment 4 times, the coking rate was 4.7 g/m2/h.
  • Example 1 was repeated for 6,12,13,24 and 48 hours with the same naphtha feed. For all the runs temperature profile is "maintained constant throughout. Typical temperature profile of a 48 hours run is shown in Figure 2. Initially the coking rate is high and decreases with time to reach an asymptotic value.
  • EXAMPLE -4 An experiment was carried out for 12 hours with a feed containing 70%> Naphtha + 30% C 5 fraction. This run was conducted to have the accelerated coking run with a feed representing naphtha characteristics. The coking rate was found to be 7 g/m2/h. Based on visual observations, the thickness of coke formed was non-uniform. Variations were found on both the top and bottom part of the samplers. The average rates of coke formation for repeated runs were reproducible. The amount of coke formed on the samplers varied with the location of the sampler in the reactor tube. The residence time of the reactants and hence conversion levels increases in the reactor tube as the distance in the reactor increased. Figure 3 shows the coke profile established from the results of 12 hours runs.
  • the x-axis of the plot is position of coke sampler from coil inlet to outlet, which reflects the residence time and they Y-axis shows the corresponding percentage of coke formed.
  • Two maxima are observed in the coke profile. The first maxima occurred at the top of second pass i.e. at lower residence time. This higher coke formation at low residence times is caused by (1) catalytic reactions on surface wall and (2) free radial reactions of micro species with the free radicals on the coke surface.
  • the micro species with molecular weights of usually 100 or less are often acetylene, ethylene and other olefins and free radical such as methyl, ethyl, phenyl or benzyl radicals.
  • Acetylene reacts with surface radicals to form aromatic rings and dehydrogenation of these rings results in more coke and more surface radicals that permit further reactions with micro species. The second maxima occurred at the top of third pass where the temperature was at maximum. This coke is formed from heavier coke precursors. Acetylene also reacts in gas phase to produce various coke precursors. Low molecular weight micro species such as benzene are the initial precursors produced and then sequence of condensation and dehydrogenation reactions occurs in gas phase to produce tar droplets and soot particles. These tar droplets adhere to the surface, decompose to form hydrogen and coke containing numerous surface radicals. More coke is formed in general with increase in temperature. However, such increase is found to be limited up to certain conversions.
  • the second set of runs comprised of a blank run i.e. run without and additive, a run with sulfur oil additive and a run with commercial sulfur additive.
  • the second set of experiments were conducted with a new set of coke samplers for all the three runs. Each experiment was carried out for 12 hours. After cooling of the furnace, the coke deposited on the coke samplers was measured. Each run was followed by a decoking run. The feed stock used was.
  • the second set of experiments were to compare the sulfur oil performance with commercial sulfur additive.
  • the coke reduction with sulfur oil additive with respect to blank run was 36%, which was similar to commercial additive.
  • EXAMPLE -7 The third set of runs comprised of a bland run i.e. run without any additive, a run with sulfur oil additive and a run with commercial sulfur additive. These runs were carried out with new set of coke samplers for each of the three runs.
  • the experiments were conducted at a dilution ratio of 0.46 of 0.46 and COT of 840 °C.
  • the composition of the naphtha feed used is given below.
  • the sulfur in the feed reduces rate of coking by reacting with metal surface to form metal sulfides and thus passivating the catalytic effect of the reactor walls.
  • EXAMPLE -8 After completion of the runs of Example 7 the reactor was cooled and spalled coke that collected in the dead space was measured. The spalled coke was collected from dead legs. Figure 6 shows the amount of spalled coke collected for the three runs. The spalling rate is higher for the runs with sulfur oil and commercial sulfur additive compared to blank run. The chemical additives alter the nature of the coke that is formed. Normally in an untreated run the coke is dense and tightly packed. With the additives in the system the ' coke is softer, less dense and more brittle and flaky.
  • EXAMPLE -9 Total sulfur analysis in gas and liquid products: the total sulfur in pyrolysis gas and liquid products of Example 6 and Example 7 was analyzed. The comparison of total sulfur present in the gas and liquid products of run with sulfur oil additive with those of commercial additive and blank run do not indicate presence of any excess sulfur in the gas and liquid product with sulfur oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de craquage thermique d'hydrocarbures dans un four à pyrolyse. L'amélioration consiste à inhiber la formation de coke sur la surface et/ou les serpentins du four à pyrolyse par ajout, dans la charge d'alimentation en hydrocarbures, de 100 à 300 ppm en poids d'une huile sulfurée qui est un mélange de disulfures organiques compris dans la plage de nombre de carbones C2-C4, et à soumettre cette charge à un craquage à une température comprise entre 820 et 855°C.
PCT/IN2004/000135 2004-05-17 2004-05-17 Procede de craquage thermique d'hydrocarbures Ceased WO2005111175A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IN2004/000135 WO2005111175A1 (fr) 2004-05-17 2004-05-17 Procede de craquage thermique d'hydrocarbures

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IN2004/000135 WO2005111175A1 (fr) 2004-05-17 2004-05-17 Procede de craquage thermique d'hydrocarbures

Publications (1)

Publication Number Publication Date
WO2005111175A1 true WO2005111175A1 (fr) 2005-11-24

Family

ID=34958566

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2004/000135 Ceased WO2005111175A1 (fr) 2004-05-17 2004-05-17 Procede de craquage thermique d'hydrocarbures

Country Status (1)

Country Link
WO (1) WO2005111175A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
WO2015136491A1 (fr) * 2014-03-14 2015-09-17 Reliance Industries Limited Procédé d'élimination du sodium contenu dans une huile disulfure
US9562006B2 (en) 2012-08-30 2017-02-07 Arkema France Preparation of symmetrical and asymmetrical disulphides by reactive distillation of mixtures of disulphides
US11021659B2 (en) 2018-02-26 2021-06-01 Saudi Arabia Oil Company Additives for supercritical water process to upgrade heavy oil
WO2021236144A1 (fr) * 2020-05-20 2021-11-25 Saudi Arabian Oil Company Conversion de sous-produits de processus mérox en produits utiles dans un procédé de raffinage intégré
WO2022165105A1 (fr) * 2021-01-28 2022-08-04 Saudi Arabian Oil Company Procédé de vapocraquage intégrant un additif d'huile de disulfure oxydé
US20220403255A1 (en) * 2019-10-31 2022-12-22 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12018220B2 (en) 2019-05-24 2024-06-25 Eastman Chemical Company Thermal pyoil to a gas fed cracker furnace
US12098338B2 (en) 2019-05-24 2024-09-24 Eastman Chemical Company Cracking c8+ fraction of pyoil
EP4237514A4 (fr) * 2020-11-02 2024-12-11 Lummus Technology LLC Four électrique pour la production d'oléfines
US12173237B2 (en) 2019-10-31 2024-12-24 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12227710B2 (en) 2019-10-31 2025-02-18 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12577188B2 (en) 2019-11-07 2026-03-17 ExxonMobil Product Solutions Company Recycle content oxo glycols

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1468873A (fr) * 1964-10-29 1967-02-10 Exxon Research Engineering Co Production d'hydrocarbures non saturés
DE1234205B (de) * 1964-08-26 1967-02-16 Metallgesellschaft Ag Verfahren zur Herstellung niedermolekularer Olefine durch thermische Spaltung von Kohlenwasserstoffen
GB1090983A (en) * 1964-10-29 1967-11-15 Exxon Research Engineering Co Production of unsaturated hydrocarbons
US5463159A (en) * 1994-03-22 1995-10-31 Phillips Petroleum Company Thermal cracking process
EP1176186A2 (fr) * 2000-07-28 2002-01-30 Atofina Chemicals, Inc. Composition pour déminuer la formation de coke dans des fours de craquage thermique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1234205B (de) * 1964-08-26 1967-02-16 Metallgesellschaft Ag Verfahren zur Herstellung niedermolekularer Olefine durch thermische Spaltung von Kohlenwasserstoffen
FR1468873A (fr) * 1964-10-29 1967-02-10 Exxon Research Engineering Co Production d'hydrocarbures non saturés
GB1090983A (en) * 1964-10-29 1967-11-15 Exxon Research Engineering Co Production of unsaturated hydrocarbons
US5463159A (en) * 1994-03-22 1995-10-31 Phillips Petroleum Company Thermal cracking process
EP1176186A2 (fr) * 2000-07-28 2002-01-30 Atofina Chemicals, Inc. Composition pour déminuer la formation de coke dans des fours de craquage thermique

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008107622A1 (fr) * 2007-02-20 2008-09-12 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbone dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
US8791314B2 (en) 2007-02-20 2014-07-29 Arkema France Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exhangers and use of same
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
US9562006B2 (en) 2012-08-30 2017-02-07 Arkema France Preparation of symmetrical and asymmetrical disulphides by reactive distillation of mixtures of disulphides
WO2015136491A1 (fr) * 2014-03-14 2015-09-17 Reliance Industries Limited Procédé d'élimination du sodium contenu dans une huile disulfure
US9790175B2 (en) 2014-03-14 2017-10-17 Reliance Industries Limited Process for the removal of sodium from di-sulfide oil
US11479729B2 (en) 2018-02-26 2022-10-25 Saudi Arabian Oil Company Additives for supercritical water process to upgrade heavy oil
US11021659B2 (en) 2018-02-26 2021-06-01 Saudi Arabia Oil Company Additives for supercritical water process to upgrade heavy oil
US12098338B2 (en) 2019-05-24 2024-09-24 Eastman Chemical Company Cracking c8+ fraction of pyoil
US12018220B2 (en) 2019-05-24 2024-06-25 Eastman Chemical Company Thermal pyoil to a gas fed cracker furnace
US20220403255A1 (en) * 2019-10-31 2022-12-22 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12173237B2 (en) 2019-10-31 2024-12-24 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12227710B2 (en) 2019-10-31 2025-02-18 Eastman Chemical Company Processes and systems for formation of recycle-content hydrocarbon compositions
US12577188B2 (en) 2019-11-07 2026-03-17 ExxonMobil Product Solutions Company Recycle content oxo glycols
US11261386B2 (en) 2020-05-20 2022-03-01 Saudi Arabian Oil Company Conversion of MEROX process by-products to useful products in an integrated refinery process
WO2021236144A1 (fr) * 2020-05-20 2021-11-25 Saudi Arabian Oil Company Conversion de sous-produits de processus mérox en produits utiles dans un procédé de raffinage intégré
EP4237514A4 (fr) * 2020-11-02 2024-12-11 Lummus Technology LLC Four électrique pour la production d'oléfines
US11459513B2 (en) 2021-01-28 2022-10-04 Saudi Arabian Oil Company Steam cracking process integrating oxidized disulfide oil additive
WO2022165105A1 (fr) * 2021-01-28 2022-08-04 Saudi Arabian Oil Company Procédé de vapocraquage intégrant un additif d'huile de disulfure oxydé

Similar Documents

Publication Publication Date Title
EP0008629B1 (fr) Procédé d'inhibition de la formation de coke de pyrolyse lors de la préparation d'oléfines
Towfighi et al. Coke formation mechanisms and coke inhibiting methods in pyrolysis furnaces
US4619756A (en) Method to inhibit deposit formation
KR102366168B1 (ko) 화학물질에 대한 원유의 통합된 열분해 및 수첨분해 장치
WO2005111175A1 (fr) Procede de craquage thermique d'hydrocarbures
JP5340914B2 (ja) フィッシャー・トロプシュ合成生成物からのプロピレン及びエチレンの製造方法
AU660867B2 (en) Phosphorothioate coking inhibitors
US5128023A (en) Method for inhibiting coke formation and deposiiton during pyrolytic hydrocarbon processing
US4378288A (en) Coking process by addition of free radical inhibitors
US5954943A (en) Method of inhibiting coke deposition in pyrolysis furnaces
KR100277412B1 (ko) 에틸렌 로 오염방지제
US4835332A (en) Use of triphenylphosphine as an ethylene furnace antifoulant
US6852213B1 (en) Phosphorus-sulfur based antifoulants
US5000836A (en) Method and composition for retarding coke formation during pyrolytic hydrocarbon processing
KR100307155B1 (ko) 열교환표면의코킹을감소시키는방법
EP0839782A1 (fr) Procédé pour l'inhibition de la formation de coke dans les fours de pyrolyse
RU2110554C1 (ru) Способ и устройство для термической переработки углеводородного сырья
US5777188A (en) Thermal cracking process
EP0207745A2 (fr) Composition et procédé pour retarder la formation de coke pendant le traitement d'hydrocarbures
EP0391620B1 (fr) Procédé de réduction des incrustations dans les fours de craquage d'éthylène
EP0852256B1 (fr) Une méthode pour inhibiter de dépot de coke avec les phosphonates/thiophonates
US4469586A (en) Heat exchanger antifoulant
Parmar et al. Effect of sulfur additives on coke formation during steam cracking of naphtha
RU2548002C1 (ru) Способ получения этилена из углеводородного сырья
EP3322773B1 (fr) Compositions, leur procédé et leurs applications

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase