EP0746597B1 - Verfahren zur verminderung der verkokung von wärmeaustauschflächen - Google Patents

Verfahren zur verminderung der verkokung von wärmeaustauschflächen Download PDF

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Publication number
EP0746597B1
EP0746597B1 EP95911204A EP95911204A EP0746597B1 EP 0746597 B1 EP0746597 B1 EP 0746597B1 EP 95911204 A EP95911204 A EP 95911204A EP 95911204 A EP95911204 A EP 95911204A EP 0746597 B1 EP0746597 B1 EP 0746597B1
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EP
European Patent Office
Prior art keywords
sulphur
silicon
heat
mixture
compounds
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
Application number
EP95911204A
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German (de)
English (en)
French (fr)
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EP0746597A1 (de
Inventor
Gerhard Zimmermann
Wolfgang Zychlinski
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.)
Vodafone GmbH
Technip Holding Benelux BV
Original Assignee
Mannesmann AG
KTI Group BV
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Publication date
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Publication of EP0746597A1 publication Critical patent/EP0746597A1/de
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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
    • 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 heat exchange surfaces in reactors and Tubular heat exchangers of plants for the implementation of hydrocarbons and other organic compounds related to the problem of Coking these exchange areas,
  • Hydrocarbons or hydrocarbon mixtures in externally heated Reactors from metallic materials are thermally cracked and the resulting ones are called cracked products after leaving the cracking furnace with pressurized water from the outside cooled as a coolant operated heat exchange apparatus.
  • the cracking furnaces are preferably made of chromium and nickel High temperature steels, the tubular heat exchangers are preferably made of low-alloy steels or boiler steel. Such devices are also used Manufacturing of other organic products, e.g. in the generation of Vinyl chloride by pyrolysis of 1,2-dichloroethane.
  • the newly formed deposits can force the decommissioning and decoking again after relatively short operating times (eg after 20 to 60 days). Since the oxidative decoking procedures used simultaneously cause a change in the material surfaces, such decoking procedures are always associated with an increase in the catalytic activity of the material surfaces, which promotes the undesirable formation of surface coke. As the number of decoking procedures to which a corresponding heat exchange surface is exposed increases, this catalytic activity increases, and the operating times between two decoking processes decrease continuously. This is undesirable from a technical as well as from an economic point of view, because this not only prevents stationary operating conditions for as long as possible, but also reduces the effective use of the system and the costs for the cleaning procedure are incurred more frequently.
  • a further improvement is provided by a coating based on silicone oil, which is subsequently thermally decomposed to produce a protective layer under very specific conditions (Chem. Techn. (Leipzig) 42 (1990) 146).
  • the process like the production of laser-induced SiO 2 surface layers, is relatively complex, and the SiO 2 layers produced in the process are not stable when the temperature changes between 750 and 1100 ° C. (outer tube wall temperature). This also applies to those passivated layers. after the British Petroleum Co. Ltd. described silica coating can be obtained (ACS Symp. Ser., New York, 1982, 202, 23-43; see also Chem. Techn. (Leipzig) 42 (1990) 146 ff).
  • the invention is therefore based on the object, new improved Propose heat exchange surfaces and a method for reducing the To provide coking with which the corresponding apparatus (equipment) an already completely installed system, both before its first installation Commissioning and after each decoking can be treated in this way.
  • the heat exchange surface is in reactors and / or Heat exchangers of plants for the implementation of hydrocarbons and other organic compounds at high temperatures in the gas phase characterized in that those coming into contact with the organic substances metallic surfaces with a mixture of silicon and sulfur containing product and a dry, versus the silicon and sulfur containing product inert gas stream, at a temperature of 300 to 1000 ° C. treated for at least 0.5 hours.
  • the product containing silicon and sulfur is preferably selected from (1) one or more volatile compounds containing silicon and sulfur, (2) one Mixture of silicon-containing volatile compounds and a mixture of volatile compounds containing sulfur and (3) a mixture of silicon and Volatile compounds containing sulfur and volatile silicon-containing compounds and / or volatile sulfur-containing compounds, the atomic ratio of Silicon and sulfur in (1), (2) or (3) are each 5: 1 to 1: 1.
  • Especially advantageous compounds are trimethylsilyl mercaptan, dimethyl sulfide, Dimethyl disulfide and bis-trimethylsilyl sulfide and mixtures thereof.
  • the treatment temperature is 800 to 1000 ° C. If the heat exchange surface treated according to the invention Metallic tube inner surface of a downstream of the tube reactor Is heat exchanger, the treatment temperature is 300 to 750 ° C. At A downstream heat exchanger can, however, still have one locally higher temperature occur. So the temperature at the impact plate on In certain cases, the input of the heat exchanger may also exceed 800 ° C, for example 875 ° C. However, it is usually in the range given above.
  • the treatment time is at least 0.5 hours and generally up to a maximum of 12 hours Hours.
  • a treatment time of less than 0.5 hours the one that occurs Effect too small for a permanent effect to be recognizable. Times of more more than 12 hours are possible, but generally uneconomical.
  • the invention is based on the surprising finding that one at the beginning Every commissioning of cracking furnaces, the reactor tubes of which are either new or Removed already deposited carbon-rich products from inside pipe surfaces are, always observed to reduce the very strong increase in coke formation effectively can, if one before the first commissioning of a cracking furnace and / or after each Recommissioning of cracking furnaces after previous steam / air decoking the pipe inner surfaces, which after commissioning with the cracking products in Come into contact with a suitable high-temperature treatment with silicon and Sulfur-containing volatile compounds.
  • the atomic ratio of silicon to sulfur can be between 5: 1 and 1: 1; a preferred range is 1: 1 to 2: 1.
  • Of the Pressure of the mixture passed through can be the usual pressure of a Crack furnace systems correspond, e.g. 0.5 - 20 bar; a preferred The range is 1 - 2 bar.
  • Another carrier gas can also be used for the system inert gas can be used.
  • the speeds of the solid, coke-like deposits which separate out on metallic materials during the pyrolysis of hydrocarbons can be measured in special vertically arranged and electrically heatable laboratory reactors if the corresponding material test specimens are suspended on a thin platinum or quartz wire inside and attached to them a thermo balance (see e.g. F.-D. Kopinke, G. Bach, G. Zimmermann: J. Anal.Appl. Pyrolysis 27 (1993) 45).
  • n-heptane was pyrolyzed as a model hydrocarbon at temperatures between 715 and 800 ° C under conditions that led to an ethylene: propylene mass ratio in the pyrolysis gas between 2.0 and 2.7.
  • FIG. 2 A typical example of the dependence of the rate of coke formation on a test specimen made of chromium-nickel steel X 8 CrNi Ti 18 10 on the reaction time in the pyrolysis of n-heptane at 780 ° C. is given by FIG. 2 for five successive coking / decoking cycles again.
  • Example 2 In the same apparatus and under analogous external conditions as in Example 1 the course of the coke formation rate on one was described preactivated test specimens made of X 8 CrNi Ti 18 10 during the pyrolysis of n-heptane 715 ° C over a test period of 60 minutes. After that, the n-heptane substituted as a pyrolysis feed by an n-heptane batch, the 85 ppm Dimethyl disulfide, a compound known as a coke inhibitor and is used industrially.
  • Fig. 3 provides information about the course of the measured Coke formation rates on the test specimen used as a function of the trial period, with a multiple change of the named products was made.
  • the measured differences in the Coke formation rates confirm the inhibitory effect of Dimethyl disulfide on coke formation on metallic material surfaces.
  • the reactor was purged with nitrogen at 715 ° C for 5 minutes.
  • the coke formation rate of r 4 ⁇ g / cm 2 ⁇ min remained almost constant over a test period of over 18 hours. Due to an arbitrary interruption of the experiment, the surface of the test specimen was cleaned after 8, 12 and 15 hours of experiment by burning off the coke with air. This did not affect the surface passivity.
  • Example 2 In the same apparatus as described in Example 1, a test specimen made of unused Incoloy 800, as mentioned in Example 4, was pretreated under the conditions specified there and the rate of coke formation during the pyrolysis of n-heptane was then monitored at 750 ° C. The pyrolysis was carried out in the presence of water vapor instead of nitrogen as a diluent. In Fig. 6, the measured coke formation rates are plotted against the test times, the pyrolysis being interrupted several times and the test specimen being decoked with air. The results show that the coke formation rate over the entire test period is at low values around 2.5 ⁇ g / cm 2 ⁇ min.
  • the measured coke formation rates are a function of Response time at at four different temperatures Trimethylsilylmethyl mercaptan treated specimens. It is can be seen that the treatment of the material surfaces according to the invention before Pyrolysis of hydrocarbons depends on the pretreatment temperature. At pretreatment temperatures above 880 ° C, coke formation becomes permanent suppressed.
  • test specimens X 8 CrNiTi 18 10 over different times with one Trimethylsilylmethyl mercaptan containing equimolar mixture of hydrogen and pretreated methane at 900 ° C.
  • the following on these test specimens the pyrolysis of n-heptane in nitrogen at 715 ° C depending on the Test duration measured coke formation rates are for four test specimens compared in Fig. 9.
  • the variation of the pretreatment time shows that at pretreatment times above 1h coke formation is equally effective over long test periods is suppressed.
  • Example 4 In the same apparatus as described in Example 1 and under the same Conditions, as indicated in Example 4, the influence of species and Composition of the compounds containing silicon and sulfur in the Pretreatment of a pre-activated test specimen with the help of one out of 50 Mol percent hydrogen and methane existing carrier gas on the Coke formation rate during n-heptane pyrolysis in nitrogen as Diluent examined.
  • the at a pretreatment temperature of 880 ° C, a pretreatment time of 60 minutes and a proportion of 0.005 mol of silicon and sulfur-containing Connection or the sum of the silicon and sulfur-containing compounds in 3 l / h of an equimolar hydrogen-methane mixture were obtained successively exposed to the reactive gas phases formed during pyrolysis and the rates of coke formation on these test specimens as a function of tracked the response time.
  • the aim of the pretreatment according to the invention is not on the Use of compounds containing silicon and sulfur at the same time is limited; rather, it is also achieved when silicon or sulfur containing compounds are used in a mixture.
  • Example 4 In the same apparatus as in Example 1 and under the same conditions as in Example 4 was the influence of the content of trimethylsilylmethyl mercaptan in the equimolar mixture of hydrogen and methane used for pretreatment determined on the coke formation rate on test specimens made of X 8 CrNiTi 18 10.
  • the hydrogen-methane mixture used for the pretreatment (3 l / h) 0.002. 0.005, 0.01 and 0.02 mol of trimethylsilylmethyl mercaptan added and the Pretreatment with 3 l of the above-mentioned conditioned Carrier gas carried out at 880 ° C over a period of 60 minutes.
  • test specimen PK 1 In a laboratory pyrolysis apparatus according to Example 1, four test specimens made of X 8 CrNiTi 18 10 were each pretreated with 3 l of a gas stream containing hydrogen and methane in equimolar amounts over a period of 60 minutes at 880 ° C., each containing 0.005 mol of tetramethylsilane (test specimen PK 1). or dimethyl sulfide (specimen PK 2) or a 1: 1 mixture of tetramethylsilane and dimethyl sulfide (specimen PK 3) or trimethylsilylmethyl mercaptan (specimen PK 4) were added. Thus, only the specimens PK 3 and PK 4 were treated according to the invention.
  • test specimens were then exposed in succession to the reactive gas phase which arises during the pyrolysis of n-heptane in a nitrogen stream at 715 ° C (residence time 1 s) and the coke formation rates on these test specimens were measured as a function of the duration of the pyrolysis tests.
  • the results are shown graphically in FIG. 10.
  • a comparison shows that only on test specimens 3 and 4 pretreated according to the invention do the low coke formation speeds typical of all test specimens be maintained over long test times. It can be concluded from the data obtained that the pretreatment according to the invention enables a significant extension of the operating time compared to a procedure without pretreatment or with a compound containing only silicon or sulfur.

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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)
  • Catalysts (AREA)
  • ing And Chemical Polishing (AREA)
  • Silicon Compounds (AREA)
EP95911204A 1994-02-21 1995-02-21 Verfahren zur verminderung der verkokung von wärmeaustauschflächen Expired - Lifetime EP0746597B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4405884A DE4405884C1 (de) 1994-02-21 1994-02-21 Wärmeaustauschfläche in Reaktoren und/oder Wärmeaustauschern und Verfahren zur Herstellung einer katalytisch desaktivierten Metalloberfläche
DE4405884 1994-02-21
PCT/DE1995/000281 WO1995022588A1 (de) 1994-02-21 1995-02-21 Verfahren zur verminderung der verkokung von wärmeaustauschflächen

Publications (2)

Publication Number Publication Date
EP0746597A1 EP0746597A1 (de) 1996-12-11
EP0746597B1 true EP0746597B1 (de) 1999-02-03

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ID=6511034

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EP95911204A Expired - Lifetime EP0746597B1 (de) 1994-02-21 1995-02-21 Verfahren zur verminderung der verkokung von wärmeaustauschflächen

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US (1) US5922192A (ru)
EP (1) EP0746597B1 (ru)
JP (1) JPH09508937A (ru)
KR (1) KR100307155B1 (ru)
CN (1) CN1105767C (ru)
AU (1) AU1889095A (ru)
CA (1) CA2182518C (ru)
CZ (1) CZ290845B6 (ru)
DE (2) DE4405884C1 (ru)
ES (1) ES2130602T3 (ru)
MX (1) MX9603427A (ru)
NO (1) NO315662B1 (ru)
PL (1) PL180515B1 (ru)
RU (1) RU2121490C1 (ru)
WO (1) WO1995022588A1 (ru)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
FR2798939B1 (fr) * 1999-09-24 2001-11-09 Atofina Reduction du cokage dans les reacteurs de craquage
US20040226861A1 (en) * 2003-05-13 2004-11-18 Szu-Jen Chien Method of separating the oil slurry from the crude oil
US8057707B2 (en) * 2008-03-17 2011-11-15 Arkems Inc. Compositions to mitigate coke formation in steam cracking of hydrocarbons
CN101880544A (zh) * 2010-07-01 2010-11-10 华东理工大学 一种抑制乙烯裂解装置结焦的复合方法
US8647415B1 (en) * 2012-07-20 2014-02-11 Lummus Technology Inc. Coke catcher
US9434612B2 (en) 2012-11-30 2016-09-06 Elwha, Llc Systems and methods for producing hydrogen gas
US9156688B2 (en) 2012-11-30 2015-10-13 Elwha Llc Systems and methods for producing hydrogen gas
CN103421531B (zh) * 2013-07-19 2015-08-12 金昌市万隆实业有限责任公司 一种减轻裂解炉管结焦方法

Family Cites Families (14)

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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
DE3005408A1 (de) * 1979-02-15 1980-08-21 Daicel Chem Semipermeables membranelement
US4410418A (en) * 1982-03-30 1983-10-18 Phillips Petroleum Company Method for reducing carbon formation in a thermal cracking process
NL8204731A (nl) * 1982-12-07 1984-07-02 Pyrotec Nv Installatie voor het thermisch kraken van een koolwaterstofuitgangsmateriaal tot alkenen, buizenwarmtewisselaar ten gebruike in zo'n installatie en werkwijze voor de vervaardiging van een buizenwarmtewisselaar.
US4692234A (en) * 1986-04-09 1987-09-08 Phillips Petroleum Company Antifoulants for thermal cracking processes
US4775459A (en) * 1986-11-14 1988-10-04 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US4842716A (en) * 1987-08-13 1989-06-27 Nalco Chemical Company Ethylene furnace antifoulants
US4835332A (en) * 1988-08-31 1989-05-30 Nalco Chemical Company Use of triphenylphosphine as an ethylene furnace antifoulant
US4900426A (en) * 1989-04-03 1990-02-13 Nalco Chemical Company Triphenylphosphine oxide as an ethylene furnace antifoulant
US5208069A (en) * 1991-10-28 1993-05-04 Istituto Guido Donegani S.P.A. Method for passivating the inner surface by deposition of a ceramic coating of an apparatus subject to coking, apparatus prepared thereby, and method of utilizing apparatus prepared thereby
US5413700A (en) * 1993-01-04 1995-05-09 Chevron Research And Technology Company Treating oxidized steels in low-sulfur reforming processes
US5358626A (en) * 1993-08-06 1994-10-25 Tetra International, Inc. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon procssing
US5656150A (en) * 1994-08-25 1997-08-12 Phillips Petroleum Company Method for treating the radiant tubes of a fired heater in a 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

Also Published As

Publication number Publication date
KR100307155B1 (ko) 2001-11-30
CA2182518A1 (en) 1995-08-24
WO1995022588A1 (de) 1995-08-24
NO963284L (no) 1996-08-06
CN1141054A (zh) 1997-01-22
MX9603427A (es) 1997-03-29
DE59505033D1 (de) 1999-03-18
PL315954A1 (en) 1996-12-23
PL180515B1 (pl) 2001-02-28
NO963284D0 (no) 1996-08-06
JPH09508937A (ja) 1997-09-09
ES2130602T3 (es) 1999-07-01
CA2182518C (en) 2000-05-16
NO315662B1 (no) 2003-10-06
EP0746597A1 (de) 1996-12-11
CZ245796A3 (en) 1997-01-15
CZ290845B6 (cs) 2002-10-16
CN1105767C (zh) 2003-04-16
RU2121490C1 (ru) 1998-11-10
DE4405884C1 (de) 1995-09-07
US5922192A (en) 1999-07-13
AU1889095A (en) 1995-09-04

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