WO2016023745A1 - Procédé de production de gaz de craquage contenant de l'éthylène et tube de craquage destiné à être utilisé dans le procédé - Google Patents

Procédé de production de gaz de craquage contenant de l'éthylène et tube de craquage destiné à être utilisé dans le procédé Download PDF

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Publication number
WO2016023745A1
WO2016023745A1 PCT/EP2015/067234 EP2015067234W WO2016023745A1 WO 2016023745 A1 WO2016023745 A1 WO 2016023745A1 EP 2015067234 W EP2015067234 W EP 2015067234W WO 2016023745 A1 WO2016023745 A1 WO 2016023745A1
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WO
WIPO (PCT)
Prior art keywords
range
canned
catalytically active
weight
tube
Prior art date
Application number
PCT/EP2015/067234
Other languages
German (de)
English (en)
Inventor
Maximilian Walter
Eric Jenne
Natalie GELDER
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2016023745A1 publication Critical patent/WO2016023745A1/fr

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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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/203—Tube furnaces chemical composition of the tubes

Definitions

  • the invention relates to a process for the production of ethylene-containing cracked gas by thermal cracking of a hydrocarbon or hydrocarbon mixture in the presence of water vapor in a can at temperatures in the range of 600 to 1000 ° C and a Spaltgasaustrittstemperatur in the range of 750 to 1000 ° C.
  • the invention further relates to a can for use in a process for the production of ethylene-containing cracking gas by thermal cracking of a hydrocarbon or hydrocarbon mixture in the presence of water vapor.
  • the thermal cracking of hydrocarbons in the presence of water vapor in a canned oven finds widespread use in ethylene plants (steam crackers), in which in addition to the ethylene, other valuable unsaturated compounds such as propylene and butadiene and Pyrolysis gasoline with a high proportion of aromatic hydrocarbons such as benzene, toluene and xylene are won.
  • steam crackers in which in addition to the ethylene, other valuable unsaturated compounds such as propylene and butadiene and Pyrolysis gasoline with a high proportion of aromatic hydrocarbons such as benzene, toluene and xylene are won.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • residence times for the hydrocarbons in the cans of the can furnace of 0.1 to 0.6 seconds (s) and outlet temperatures of the cracked gases from the cans of more than 750 ° C., generally between 800 and 1000 ° C., are preferred , complied. See, e.g. D. Glietenberg et al., Ullmanns Encyklopadie der ischen Chemie, 4th ed., Volume 8,
  • the canned oven must be turned off and the crevices of the deposits, esp. The coke, freed.
  • the split tubes and associated moldings are usually freed of the deposits with a water vapor / air mixture or even only with air at temperatures of 700 to 1000 ° C, as for example. in EP 36151 A1 (BASF AG).
  • Catalytically active coatings on the inner surface of cans or canned systems which can significantly reduce carbonaceous deposits, especially coke deposits, and convert these deposits, especially coke, into CO and CO2, e.g. Camol TM.
  • SFT® Swirl Flow Tubes®
  • Catalytically active coatings e.g. CAMOL TM have the disadvantage of all catalytic processes of being contaminated during operation with impurities, e.g. Sulfur compounds, and indefinite operating conditions in the canned oven lose activity.
  • US 5,242,574 A (Institute Francais du Petrole) relates to thermal vapor phase cracking and dehydrogenation of hydrocarbons in a honeycomb type reactor in a pyrolysis zone heated with a "heating liquid", in the presence of a special alloy 66-82 wt% Ni, 14-18 wt% Cr and 4-6 wt% Al.
  • WO 2014/092944 A1 (General Electric Company) describes the use of metallic cracker coils with an anti-coking catalyst layer, in particular perovskite (CaTiO 3), and an alumina barrier layer in the vapor-phase cracking of hydrocarbons.
  • the object of the present invention while overcoming disadvantages of the prior art, is to provide an improved economical process for the production of ethylene-containing cracked gas.
  • the process should also be particularly advantageous if, in the inlet region of catalytic canned systems, there is a temperature range at which the catalytic coating is not or only insufficiently restored after decoking, i. not or only insufficiently regenerated, can be.
  • the can in the region through which it flows first comprises a steel which is an alloy containing 25-35% by weight chromium, 25-55% by weight nickel, 2-6% by weight aluminum and 10-30% by weight. % Iron, thereby reducing carbonaceous deposits in the pipe,
  • a canned pipe has accordingly been found for use in a process for the production of ethylene-containing cracked gas by thermal cracking of a hydrocarbon or hydrocarbon mixture in the presence of water vapor, esp.
  • the canned in first to be flown A steel comprising an alloy containing 25-35% by weight of chromium, 25-55% by weight of nickel, 2-6% by weight of aluminum and 10-30% by weight of iron, whereby carbonaceous deposits are reduced in the pipe in the manufacturing process for fission gas, and the gap in the subsequently flowing through area on the inner surface has a catalytically active coating which reduces carbonaceous deposits in the pipe in the production process for fission gas.
  • the can in the region to be flown through does not comprise a steel as in the region to be flowed through first, but another steel which is particularly 0 to ⁇ 0.5% by weight, in particular 0 to ⁇ 0.1% by weight.
  • a steel as in the region to be flowed through first, but another steel which is particularly 0 to ⁇ 0.5% by weight, in particular 0 to ⁇ 0.1% by weight.
  • Contains aluminum an example is an alloy containing 25-45 wt .-% chromium, 30- 60 wt .-% nickel and 10-25 wt .-% iron; (The alloy may, for example, also niobium (eg 0.1 to 2 wt .-%) and / or carbon (eg 0.1 to 1, 5 wt .-%) and / or silicon (eg 0.5 to 2.5 Wt .-%) and / or manganese (eg 0.1 to 2 wt .-%) contain; typical further trace elements (eg in each case 0.01 to 0.5
  • steel comprehensive and partly inside to be provided with a catalytically active coating crevices may be straight tubes or curved tubes, such as coils.
  • the term 'split tube' in particular also includes molded parts connected to the split tube, such as Y-pieces, collectors, reversal bends, reducers.
  • Canned pipe plus connected moldings are also called canned system.
  • Canned systems can be provided e.g. 1 to 20 reversal bends (or even more), especially e.g. 1 to 1 1 reverse bends, and corresponding to 2 to 21 (or correspondingly more), especially 2 to 12, passports.
  • Passes in an initially traversed area can also be divided into several, e.g. 2 to 25, parallel tubes and possibly reversal bends be divided.
  • the Linde PYROCRACK® 4-2 Canned Pipe System (Fig. 2) consists of 6 passports and 5 reversing bends, with 4 passages divided into 2 parallel pipes in an initially flown-through area.
  • the thermal cleavage of the hydrocarbon or hydrocarbon mixture is preferably carried out in the first flow-through range at temperatures in the range of 600 to 800 ° C and in the thereafter flowed through at temperatures in the range of 700 to 1000 ° C.
  • the weight ratio of water vapor to the hydrocarbon used or to the hydrocarbon mixture used is in the thermal cracking particularly in the range of 0.1 to 1, preferably in the range of 0.2 to 0.8, and more particularly in the range of 0.3 to 0th , 7th
  • the pressure in the can is in the thermal cleavage especially 1, 5 to 5 bar, especially 1, 6 to 2.5 bar.
  • the can in the region through which it flows first comprises a high-alloyed steel which forms aluminum oxide on the inner side of the tube. This has the effect of reducing carbonaceous deposits in the pipe.
  • the split tube was made in the first through-flow region by a centrifugal casting process.
  • the molded parts of the can system were produced by means of a casting process from the same steels.
  • the steel is a Cr, Ni and Al-containing steel, i. Cr-Ni-Al-Fe alloy.
  • the alloy containing Cr, Ni, Al and Fe may also contain, for example, niobium (eg 0.1 to 1% by weight) and / or carbon (eg 0.1 to 1% by weight); Typical further trace elements (eg in each case 0.01 to 0.5% by weight) may be: Mn, W, Si, Co, Mo and / or Ti.
  • niobium eg 0.1 to 1% by weight
  • carbon e.g 0.1 to 1% by weight
  • Typical further trace elements eg in each case 0.01 to 0.5% by weight
  • Mn, W, Si, Co, Mo and / or Ti may be found in the Information Data Sheet, Centrailoy® HT E, Schmidt + Clemens GmbH + Co. KG, Sept. 2009, Rev. 01. See also the other references cited above.
  • the formation of aluminum oxide on the inner surface of the tube takes place in the presence of oxygen, especially at elevated temperature, e.g. B.> 100 ° C, in particular> 500 ° C, for example in the range of 550 to 1000 ° C instead.
  • elevated temperature e.g. B.> 100 ° C, in particular> 500 ° C, for example in the range of 550 to 1000 ° C instead.
  • the can in the region through which it flows first comprises a high-alloy steel which forms aluminum oxide on the inner surface of the pipe and in the region through which it flows, it has a catalytically active coating on the inner surface.
  • the catalytically active coating preferably contains manganese (Mn), especially manganese, in an oxidation state in the range from 2 to 7, further especially in the form of a manganese oxide, further especially in the form of MnO, ⁇ 2 ⁇ 3, MnC "2, Mn 2 C and / or ⁇ 3 ⁇ 4 , especially in the form of MnO.
  • Mn manganese
  • CAMOL TM coatings as e.g. in the BASF publication "CAMOL TM Catalytic Coatings for Steam cracker furnace tubes", BF-9657 3/12. These are the so-called “Low-Catalytic Gasification (LCG) Coating” and the so-called “High-Catalytic Gasification (HCG) Coating”.
  • LCG Low-Catalytic Gasification
  • HCG High-Catalytic Gasification
  • Comparative Example 1 In a canned oven containing four canned systems, a mixture of 2.2 th of a gasoline fraction (naphtha) having a boiling range of 40 to 180 ° C and 1, 0 t / h of steam were passed per canned system and at a cracking tube outlet temperature of up to 840 ° C thermally split.
  • naphtha a gasoline fraction having a boiling range of 40 to 180 ° C and 1, 0 t / h of steam were passed per canned system and at a cracking tube outlet temperature of up to 840 ° C thermally split.
  • the cracking tubes were internally provided with a catalytically active coating containing manganese, as described in the BASF publication "CAMOL TM catalytic coatings for steam cracker furnace tubes", BF-9657 3/12.
  • LCG 'Low-Catalytic Gasification
  • HCG High-Catalytic Gasification
  • the tube wall temperature at the measured location in the canned system eventually increased to 1 100 ° C after several months running time, the highest tube wall temperature used for the material and coating of this canned system.
  • the differential pressure of the flow nozzles in the inlet of the can system could be reduced to the minimum applied differential pressure limit of 0.3 bar.
  • example 1 In a canned oven containing four canned systems, a mixture of up to 2.2 t / h of a gasoline fraction (naphtha) having the boiling range of 40 to 180 ° C and 1, 0 t / h of steam are passed per canned system and at a crevice tube outlet temperature thermally split up to 840 ° C.
  • a canned system consists of 18 parallel, vertical inlet tubes, which are flowed through from top to bottom and merged into a manifold. From there, the fission gas is led out of the furnace in 2 parallel, vertical outlet pipes, which are flowed through from bottom to top.
  • the canned system is constructed analogously to a selective 2-pass canned system with the designation SRT®-V from CB & I (Lummus); see. Fig. 3.
  • SRT®-V from CB & I (Lummus); see. Fig. 3.
  • the cracked gas from each of two split-tube systems is cooled in a downstream split-gas cooler.
  • the split tubes are made in the front, first through-flow region of the can system from a high-alloy, produced by centrifugal casting, forming on the inner surface alumina steel, as described in the publication: Information Data Sheet,
  • the aluminum oxide-forming high-alloy steel is provided, starting from the top, to a length of 40% of the total length of the can system.
  • the canned system is internally provided with a catalytically active coating containing manganese and tungsten, namely, High-Catalytic Gasification (HCG) coating, as described in the BASF publication "CMOL TM catalytic Coatings for steam crackers furnace tubes ", BF-9657 3/12.
  • HCG High-Catalytic Gasification
  • the manually measured pipe wall temperature at the outlet of the canned system can be 940 to 980 ° C.
  • the tube wall temperature at the measured point in the last flowed through region of the crevice tube system can finally rise after several months of running up to 1 100 ° C, the highest pipe wall temperature applied to the material and the coating at this point of the canned system.
  • the differential pressure of the flow nozzles in the inlet of the can system can be reduced to the minimum applied differential pressure limit of 0.3 bar.
  • the hydrocarbon stream is interrupted by the canned oven and the canned systems separated from the rest of the process and freed from coke by means of oxygen.
  • a temperature in the range of 760 to 825 ° C and a pressure of 1, 05 to 3 bar over a total period of 60 hours at the beginning of a water steam / air mixture passed into the gap tubes, which is changed in the further course by reducing the amount of steam so that the amount of air in the mixture of initially 10 wt .-% to 70 wt .-% increases.
  • Pipe inner surface Alumina-forming "steel”, in particular "alloy containing 25-35 wt .-% chromium, 25-55 wt .-% nickel, 2-6 wt .-% aluminum and 10-30 wt .-% iron", and "Catalytically active coating” carbon deposits are optimally reduced in the entire range of the canned system, so that extended by many days to several weeks extended production times of the canned oven, compared to the respective installed individual technology.

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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)

Abstract

L'invention concerne un procédé de production de gaz de craquage contenant de l'éthylène par craquage thermique d'un hydrocarbure ou d'un mélange d'hydrocarbures en présence de vapeur d'eau dans un tube de craquage à des températures dans la plage de 600 à 1000 °C et une température de sortie du gaz de craquage dans la plage de 750 à 1000 °. Le tube de craquage comprend, dans la zone traversée en premier par le courant un acier qui est un alliage contenant 25-35 % massiques de chrome, 25-55 % massiques de nickel, 2-6 % massiques d'aluminium et 10-30 % massiques de fer, les dépôts contenant du carbone dans le tube étant ainsi réduits et le tube de craquage possède, sur la surface intérieure dans la zone qui est ensuite traversée par le courant, un revêtement à activité catalytique qui réduit les dépôts contenant du carbone dans le tube. Le tube de craquage ne possède pas le revêtement à activité catalytique sur la surface intérieure dans la zone traversée en premier par le courant. L'invention concerne également un tube de craquage destiné à être utilisé dans le procédé.
PCT/EP2015/067234 2014-08-13 2015-07-28 Procédé de production de gaz de craquage contenant de l'éthylène et tube de craquage destiné à être utilisé dans le procédé WO2016023745A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14180874.1 2014-08-13
EP14180874 2014-08-13

Publications (1)

Publication Number Publication Date
WO2016023745A1 true WO2016023745A1 (fr) 2016-02-18

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PCT/EP2015/067234 WO2016023745A1 (fr) 2014-08-13 2015-07-28 Procédé de production de gaz de craquage contenant de l'éthylène et tube de craquage destiné à être utilisé dans le procédé

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242574A (en) * 1989-06-08 1993-09-07 Institut Francais Du Petrole Use of nickel-based alloys in a process for the thermal cracking of a petroleum charge and reactor for performing the process
US20110272070A1 (en) * 2008-10-13 2011-11-10 Schmidt + Clemens Gmbh + Co. Kg Nickel-chromium-alloy
WO2014092944A1 (fr) * 2012-12-13 2014-06-19 General Electric Company Revêtements de catalyseur anti-encrassement au moyen d'une couche barrière d'alumine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242574A (en) * 1989-06-08 1993-09-07 Institut Francais Du Petrole Use of nickel-based alloys in a process for the thermal cracking of a petroleum charge and reactor for performing the process
US20110272070A1 (en) * 2008-10-13 2011-11-10 Schmidt + Clemens Gmbh + Co. Kg Nickel-chromium-alloy
WO2014092944A1 (fr) * 2012-12-13 2014-06-19 General Electric Company Revêtements de catalyseur anti-encrassement au moyen d'une couche barrière d'alumine

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