EP2125998A1 - Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exchangers and use of same - Google Patents
Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exchangers and use of sameInfo
- Publication number
- EP2125998A1 EP2125998A1 EP08762128A EP08762128A EP2125998A1 EP 2125998 A1 EP2125998 A1 EP 2125998A1 EP 08762128 A EP08762128 A EP 08762128A EP 08762128 A EP08762128 A EP 08762128A EP 2125998 A1 EP2125998 A1 EP 2125998A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cracking
- additive
- ppm
- organic compounds
- hydrocarbons
- 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
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
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
Definitions
- the present invention relates to the field of cracking hydrocarbons or other organic compounds and more particularly relates to a process for reducing coking on the walls of cracking reactors and heat exchangers used to cool the compounds resulting from the reaction of cracking.
- the tubular reactors used are preferably made of steels rich in chromium and nickel, whereas the heat exchangers, subjected to less severe stresses, consist of carbon steels or low alloyed steels. This same type of equipment is also encountered to produce other organic compounds such as vinyl chloride by pyrolysis of 1,2-dichloroethane.
- the hydrocarbon cracking units such as steam crackers are thus frequently stopped to undergo decoking cycles (after 20 to 60 days Operating).
- oxidative decoking treatment leads to an increase in the catalytic activity of the cracked metal surface, which increases the rate of coke formation.
- the operating time decreases and the annual number of decoking operation increases. This long-term effect is technically and economically damaging as maintenance costs become heavier with the age of the unit for a lower annual rate of operation.
- No. 4,116,812 discloses a process for inhibiting coke using dithiol-thione organosulfur-containing additives at temperatures of between 260 and 815 ° C.
- US Pat. No. 5,463,159 discloses a method for treating ovens used in the production of coke. ethylene with hydrogen sulphide (H 2 S) generating compounds to reduce coke formation.
- the preferred H 2 S generating compound is dimethyl sulfide (DMS).
- No. 5,616,236 teaches a method of inhibiting coke and CO by treating the steam cracker tubes with sulfur compounds in the presence of hydrogen, the sulfur compounds being of the sulphide or disulfide type, the DMS and the DMDS being particularly preferred.
- No. 5,954,943 describes a method for reducing the coke deposition in cracking furnaces by using a mixture of sulfur and phosphorus compounds with an S / P molar ratio greater than or equal to 5.
- EP 976,726 A1 is concerned with masked odor DMDS indicated in [0002] that it can be used as a feed additive in a steam cracker.
- WO 2005/111175 discloses a process for the thermal cracking of hydrocarbon compounds and the use in admixture as an antico-agent of a mixture of organic disulfides of carbon rank between 2 and 4 called "sulfur oil” or “disulfide oil (DSO)".
- the preferred mixture is a mixture of alkyl disulfides wherein the alkyl groups are methyl and ethyl and where the typical sulfur content is 60%.
- the present invention relates to novel additives for reducing the formation of coke and / or carbon monoxide in thermal cracking units and heat exchangers consisting essentially of diethyldisulphide (DEDS) or dipropyldisulphide (s) (DPDS) or dibutyldisulphide ( s)
- DEDS diethyldisulphide
- DPDS dipropyldisulphide
- s dibutyldisulphide
- the anti-coke and / or anti-CO additive consists essentially of DEDS. According to a preferred form of the invention, the anti-coke and / or anti-CO additive consists essentially of DPDS.
- the anti-coke and / or anti-CO additive consists essentially of DBDS.
- the term "essentially consists of” means contains less than 20,000 ppm impurities, preferably less than 10,000 ppm impurities, and desirably less than 5,000 ppm impurities.
- impurities is meant traces of one or more organo-sulfur compounds which can be represented by the formula RS n R 'with n representing the average rank of sulfur ranging from 1 to 10, and R and R' representing H or an alkyl, cycloalkyl, aryl, linear or branched C 1 -C 24 chain, such as for example DMDS, dimethyl sulfide, methyl mercaptan, ethyl mercaptan, DPDS and / or DBDS when the anti-coke and anti-CO agent essentially consists of DEDS.
- organo-sulfur compounds which can be represented by the formula RS n R 'with n representing the average rank of sulfur ranging from 1 to 10, and R and R' representing H or an alkyl, cycloalkyl, aryl, linear or branched C 1 -C 24 chain, such as for example DMDS, dimethyl sulfide, methyl mercaptan, ethyl mer
- dipropyl disulphide s
- DBDS dibutyldisulphide
- the anti-coke and / or anti-CO additives according to the invention which make it possible, by means of their thermal decomposition, to increase the yield of olefins of the final product are of particular interest to manufacturers insofar as their decomposition makes it possible to produce olefins. such as ethylene, propylene and butene, respectively, thus increasing the olefin yield of the final product at the exit of the cracking furnace.
- the invention has for object 2 nd method for reducing coking and / or carbon monoxide on the metal walls of a hydrocarbon cracking reactor and / or other organic compounds and on the metal walls of a heat exchanger placed after the cracking reactor, characterized in that the metal surfaces coming into contact with the organic substance to be cracked are pretreated with a stream of water vapor containing in particular the additive according to the invention, at a temperature of between 300 and 1.100 ° C., preferably between 400 and 700 ° C. for the heat exchanger and preferably between 750 and 1.050 ° C. for the cracking tube, for a period of time. between 0.5 and 12 hours, preferably between 1 and 6 hours.
- the concentration of the additive according to the invention in the vector fluid consisting of steam alone or mixed with an inert gas can generally range from 50 to 5,000 ppm. mass. Preferably, this concentration is between 100 and 3,000 mass ppm.
- the pressure of the fluid vector is generally equal to that usually used in cracking furnaces (between 1 and 20 bar absolute, preferably between 1 and 5 bar absolute).
- the pretreatment according to the invention can be implemented in any new cracking unit or in any existing unit after each decoking operation. It is particularly easy to set up in steam cracking units since, as a carrier gas, it uses water vapor, a fluid already available usually in said units.
- the invention also relates to 3 rd object a hydrocarbon cracking process and / or other organic compounds in which the additive according to the invention is added during the cracking at the expense of cracking organic compounds generally carried out between 600 and 1000 0 C, preferably between 650 and 900 ° C.
- This addition can be made at lower temperature, in the liquid feed, before its preheating and vaporization and / or during the preheating phase, up to 600 ° C.
- this addition can be carried out in steam, between 150 and 650 ° C.
- the concentration of additive according to the invention is chosen so that the concentration of sulfur in the hydrocarbons and / or the organic compounds to be cracked is preferably between 10 and 1000 ppm by weight, and advantageously between 20 and 400 ppm by mass.
- DEDS additive according to the invention
- Pyrolysis tests are carried out in an oven of up to 1,000 ° C. by introducing the additive at a flow rate of 0.5 ml / h, water with a flow rate of 13.5 ml / h and under a flow of hydrogen of 40 L / h.
- the residence time is about 0.5 s.
- the gases are analyzed by chromatography.
- the table below shows the mass percentages of hydrocarbons (methane (CH 4 ), ethane (C 2 H 6 ) and ethylene (C 2 H 4 )) relative to the total mass of hydrocarbons obtained by thermal decomposition of each additives tested at a temperature of 800 ° C., a typical value in steam-cracking units.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0753380A FR2912757B1 (en) | 2007-02-20 | 2007-02-20 | ADDITIVE FOR REDUCING COKAGE AND / OR CARBON MONOXIDE IN CRACK REACTORS AND HEAT EXCHANGERS, USE THEREOF |
US94926607P | 2007-07-12 | 2007-07-12 | |
PCT/FR2008/050281 WO2008107622A1 (en) | 2007-02-20 | 2008-02-20 | Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exchangers and use of same |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2125998A1 true EP2125998A1 (en) | 2009-12-02 |
Family
ID=38521625
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08762128A Ceased EP2125998A1 (en) | 2007-02-20 | 2008-02-20 | Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exchangers and use of same |
Country Status (5)
Country | Link |
---|---|
US (1) | US8791314B2 (en) |
EP (1) | EP2125998A1 (en) |
CA (1) | CA2678153C (en) |
FR (1) | FR2912757B1 (en) |
WO (1) | WO2008107622A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2724389A1 (en) * | 2010-12-08 | 2012-06-08 | Nova Chemicals Corporation | In situ removal of iron complexes during cracking |
CA2962667C (en) | 2017-03-30 | 2024-03-19 | Nova Chemicals Corporation | Decoking process |
US11021659B2 (en) | 2018-02-26 | 2021-06-01 | Saudi Arabia Oil Company | Additives for supercritical water process to upgrade heavy oil |
CA3033604C (en) | 2019-02-12 | 2022-12-13 | Michael KOSELEK | Decoking process |
US10995278B2 (en) * | 2019-09-10 | 2021-05-04 | Saudi Arabian Oil Company | Disposal of disulfide oil compounds and derivatives in delayed coking process |
US11306263B1 (en) * | 2021-02-04 | 2022-04-19 | Saudi Arabian Oil Company | Processes for thermal upgrading of heavy oils utilizing disulfide oil |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1234205B (en) * | 1964-08-26 | 1967-02-16 | Metallgesellschaft Ag | Process for the production of low molecular weight olefins by thermal cracking of hydrocarbons |
GB1090983A (en) * | 1964-10-29 | 1967-11-15 | Exxon Research Engineering Co | Production of unsaturated hydrocarbons |
US4116812A (en) | 1977-07-05 | 1978-09-26 | Petrolite Corporation | Organo-sulfur compounds as high temperature antifoulants |
US4511405A (en) | 1982-09-30 | 1985-04-16 | Reed Larry E | Antifoulants for thermal cracking processes |
US4507196A (en) | 1983-08-16 | 1985-03-26 | Phillips Petroleum Co | Antifoulants for thermal cracking processes |
US4686201A (en) | 1984-07-20 | 1987-08-11 | Phillips Petroleum Company | Antifoulants comprising tin antimony and aluminum for thermal cracking processes |
US4552643A (en) | 1985-01-22 | 1985-11-12 | Phillips Petroleum Company | Antifoulants for thermal cracking processes |
US4613372A (en) | 1985-01-22 | 1986-09-23 | Phillips Petroleum | Antifoulants for thermal cracking processes |
US4687567A (en) | 1986-04-09 | 1987-08-18 | Phillips Petroleum Company | Antifoulants for thermal cracking processes |
US4804487A (en) | 1986-04-09 | 1989-02-14 | Phillips Petroleum Company | Antifoulants for thermal cracking processes |
US4666583A (en) | 1986-04-09 | 1987-05-19 | Phillips Petroleum Company | Antifoulants for thermal cracking processes |
FR2628437B1 (en) * | 1988-03-14 | 1992-12-31 | Inst Francais Du Petrole | PROCESS FOR THE HEAT TREATMENT OF HYDROCARBON CHARGES IN THE PRESENCE OF POLYSULFIDES AND HYDROGEN DONORS |
US5015358A (en) | 1990-08-30 | 1991-05-14 | Phillips Petroleum Company | Antifoulants comprising titanium for thermal cracking processes |
US5463159A (en) * | 1994-03-22 | 1995-10-31 | Phillips Petroleum Company | Thermal cracking process |
US5565087A (en) | 1995-03-23 | 1996-10-15 | Phillips Petroleum Company | Method for providing a tube having coke formation and carbon monoxide inhibiting properties when used for the thermal cracking of hydrocarbons |
US5954943A (en) * | 1997-09-17 | 1999-09-21 | Nalco/Exxon Energy Chemicals, L.P. | Method of inhibiting coke deposition in pyrolysis furnaces |
EP0976762A1 (en) | 1998-07-29 | 2000-02-02 | Daesang Corporation | Crystallization of Alpha-L-aspartyl-L-phenylalanine methyl ester |
FR2798939B1 (en) * | 1999-09-24 | 2001-11-09 | Atofina | REDUCING COKAGE IN CRACKING REACTORS |
WO2001096499A1 (en) * | 2000-06-10 | 2001-12-20 | Sk Corporation | The method for using disulfide mixture as a sulfiding agent |
US6673232B2 (en) * | 2000-07-28 | 2004-01-06 | Atofina Chemicals, Inc. | Compositions for mitigating coke formation in thermal cracking furnaces |
US6784329B2 (en) * | 2002-01-14 | 2004-08-31 | Chevron U.S.A. Inc. | Olefin production from low sulfur hydrocarbon fractions |
WO2005111175A1 (en) * | 2004-05-17 | 2005-11-24 | Indian Petrochemicals Corporation Limited | Process for thermal cracking hydrocarbons |
-
2007
- 2007-02-20 FR FR0753380A patent/FR2912757B1/en active Active
-
2008
- 2008-02-20 CA CA2678153A patent/CA2678153C/en active Active
- 2008-02-20 EP EP08762128A patent/EP2125998A1/en not_active Ceased
- 2008-02-20 WO PCT/FR2008/050281 patent/WO2008107622A1/en active Application Filing
- 2008-02-20 US US12/526,317 patent/US8791314B2/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2008107622A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2008107622A8 (en) | 2008-11-06 |
FR2912757A1 (en) | 2008-08-22 |
CA2678153A1 (en) | 2008-09-12 |
CA2678153C (en) | 2013-06-11 |
US8791314B2 (en) | 2014-07-29 |
WO2008107622A1 (en) | 2008-09-12 |
US20100069695A1 (en) | 2010-03-18 |
FR2912757B1 (en) | 2010-11-19 |
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