EP2557142A1 - Procédé de craquage d'hydrocarbures - Google Patents
Procédé de craquage d'hydrocarbures Download PDFInfo
- Publication number
- EP2557142A1 EP2557142A1 EP11009116A EP11009116A EP2557142A1 EP 2557142 A1 EP2557142 A1 EP 2557142A1 EP 11009116 A EP11009116 A EP 11009116A EP 11009116 A EP11009116 A EP 11009116A EP 2557142 A1 EP2557142 A1 EP 2557142A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbon
- hydrocarbons
- fraction
- thermal
- 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.)
- Withdrawn
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- the invention relates to a process for the preparation of olefins from a liquid hydrocarbon-containing feed by means of thermal decomposition, wherein the hydrocarbons of the hydrocarbon-containing feed to a maximum of 3% unsaturated hydrocarbons, wherein the resulting in the thermal cracking raw gas is removed from impurities, then into the individual components , in particular hydrocarbons, is decomposed and wherein the raw gas comprises the constituents ethylene and propylene.
- hydrocarbon-containing use is understood as meaning hydrocarbon-containing inserts which mainly contain relatively long-chain saturated hydrocarbons, for example naphtha, atmospheric gas oil, kerosene, hydrogenated or unhydrogenated heavy / high-boiling hydrocarbon mixtures.
- Hydrocarbon-containing inserts which mainly contain relatively long-chain saturated hydrocarbons, for example naphtha, atmospheric gas oil, kerosene, hydrogenated or unhydrogenated heavy / high-boiling hydrocarbon mixtures.
- Unsaturated hydrocarbons in the context of the application are not understood to mean aromatic hydrocarbons having at least one double bond.
- the products are produced by cleavage of hydrocarbon-containing inserts.
- the hydrocarbon-containing inserts are present either in the liquid or gaseous phase and are converted by means of thermal or catalytic cleavage with or without steam into shorter-chain hydrocarbons.
- the resulting mixture in the cleavage of predominantly shorter-chain olefins is referred to as cracking gas or crude gas.
- the raw gas In the cleavage of a liquid hydrocarbon-containing feed, the raw gas is usually performed as an insert in an oil scrubber. In the oil scrubbing, the crude gas is cooled and remaining longer-chain hydrocarbons, such as coke particles and heavy oil components, washed out of the raw gas. Subsequently, the crude gas is passed for further purification and cooling in a water wash and compressed in the crude gas compression. Subsequently, will the raw gas according to the prior art in a lye wash of other impurities, such as carbon dioxide and hydrogen sulfide, freed and dried.
- the purified and dried crude gas now consists of a mixture of the desired olefin products and by-products. In order to utilize the desired olefin products, the mixture must be separated into the individual olefin components. The separation of the raw gas into the individual components is known in the art.
- the thermal decomposition of such liquid hydrocarbons is carried out in so-called cracking furnaces, which have a fired radiation zone and a convection zone.
- a fuel is burned in the radiation zone and the gap tubes leading through the radiation zone are heated by means of thermal radiation.
- the flue gases produced during firing are led out of the cracking furnace through the convection zone.
- the heat of the executed flue gases is typically used in heat exchangers for evaporation and overheating of the liquid hydrocarbon-containing insert and the process steam and for high pressure steam overheating or similar process tasks.
- the present invention has for its object to provide a method of the type mentioned in such a way that the efficiency of the method is increased. Furthermore, the present invention has the object to design the method such that the coking minimized in the cans and thus longer maturities between the cleaning shutdowns can be achieved.
- unsaturated hydrocarbons are added to the hydrocarbon-containing feed before the thermal cracking.
- the composition of the feed stream of the thermal cleavage changes.
- the relative proportion of saturated hydrocarbons in the feed stream of the thermal cracking becomes smaller.
- the inventive admixture of unsaturated hydrocarbons in the feed stream of the thermal cleavage allows an economic operation of thermal cleavage in milder conditions than in the prior art.
- the resulting mild conditions lead to a significantly lower coking of the cracking tubes, whereby the necessary purification phase of the cracking furnaces in much longer intervals is necessary.
- the coking is burned off during the cleaning phases. During these purification phases no thermal cleavage takes place and thus no value product is produced.
- the proportion of unsaturated hydrocarbons, based on the total weight of the hydrocarbons, after admixture before the thermal decomposition is between 3% by weight and 40% by weight, preferably between 5% by weight and 30% by weight, particularly preferably between 15% by weight. and 25% by weight.
- the liquid hydrocarbon-containing feed is mixed before the thermal cleavage with a C 4 fraction, wherein the C 4 fraction contains unsaturated hydrocarbons having four carbon atoms and separated from the resulting in the thermal cracking crude gas and for mixing with the hydrocarbon-containing Use was led back.
- the liquid hydrocarbonaceous feed is mixed with a C 5-8 fraction prior to thermal cracking, the C 5-8 fraction containing unsaturated hydrocarbons having between 5 and 8 carbon atoms, preferably 5 unsaturated hydrocarbons Containing carbon atoms, and was separated from the resulting in the thermal cracking crude gas and recycled for mixing with the hydrocarbon-containing use.
- the C 5 fraction from the C 6-8 fraction and to recycle only one or both fractions for mixing.
- a hydrocarbon fraction consisting of hydrocarbons having n carbon atoms is referred to as the C n fraction. If this hydrocarbon fraction consists of hydrocarbons having at least n carbon atoms, the hydrocarbon fraction is referred to as the C n + fraction.
- a fraction of hydrocarbons with a maximum of n carbon atoms is referred to as C n- fraction. Where n stands for the natural numbers 1, 2, 3, 4 ...
- the crude gas is cooled after the thermal cracking, freed of impurities and fed into a decomposition part.
- a C 4+ fraction is separated from the crude gas.
- the C 4+ fraction is further separated into a C 4 fraction and a C 5+ fraction.
- the C 4 fraction is preferably subjected to extraction, wherein butadiene is selectively separated and recovered as desired product.
- the remaining C 4 fraction which contains a large proportion of butenes, ie unsaturated hydrocarbons, is preferably recycled and mixed with the hydrocarbon-containing feed.
- the C 5+ fraction is preferably subjected to typical gasoline processing with selective catalytic hydrogenations and aromatics extraction, advantageously separating aromatic hydrocarbons and a C 9+ fraction.
- the resulting C 5-8 fraction contains mainly pentenes as unsaturated hydrocarbons.
- the recirculated C 4 fraction and the recycled C 5-8 fraction are in the liquid state. Therefore, they can be readily mixed directly with the liquid hydrocarbonaceous feed.
- the cracking conditions are adjusted such that the crude gas formed as a cracking product propylene and ethylene in a propylene to ethylene ratio of about 0.8 kg / kg, preferably between 0.9 kg / kg and 1.5 kg / kg, more preferably between 1.1 kg / kg and 1.4 kg / kg, in particular of 1.3 kg / kg. It has been shown that the market price of propylene increases more than the price of ethylene. As a result, the economy of the method is further increased in this embodiment of the invention.
- the thermal cracking is carried out in the radiation zone of a cracking furnace, wherein the hydrocarbon-containing feed is previously evaporated and mixed with water vapor and guided in crevices through the fired radiation zone of the cracking furnace, wherein the radiation zone is heated so that the resulting raw gas at the outlet of the cracking tubes a Temperature between 720 ° C and 800 ° C has.
- Carrying out the thermal cracking at an outlet pressure in the can tubes between 2.5 bar absolute and 4 bar absolute has also proven to be advantageous as the mixture of steam and hydrocarbon-containing feed with a mass ratio of water vapor to hydrocarbons in the hydrocarbonaceous use between 0.15 kg / kg and 0.45 kg / kg, preferably between 0.15 kg / kg and 0.35 kg / kg.
- the mentioned cleavage conditions allow in particular to carry out the thermal cleavage under mild conditions which lead to the reduction of coking.
- Carrying out at the increased pressure in the range from 2.5 bar absolute to 4 bar absolute compared to the prior art allows the saving of a compression stage of the raw gas, whereby both investment and energy costs are reduced.
- the lower amount of steam compared to the prior art also leads to a reduction in the energy consumption of the process, since less water vapor has to be generated or overheated.
- the present invention makes it possible in particular to significantly improve the cost-effectiveness of a method mentioned at the outset.
- the number of necessary cleaning cycles of the split tubes is reduced.
- FIG. 1 shows an embodiment of the invention.
- a liquid hydrocarbonaceous feed (naphtha) 1 is fed into a cracking furnace 2.
- the liquid hydrocarbonaceous feed is vaporized and mixed with water vapor in a mass ratio of steam to hydrocarbons between 0.15 and 0.35 (not shown).
- the cracking conditions in the cracking furnace 2 are adjusted such that in the raw gas 3, ethylene and propylene are formed in a ratio of propylene to ethylene of more than 1.
- the temperatures of the mixture of hydrocarbon-containing use and water vapor at the outlet of the cans is between 720 ° C and 800 ° C at a pressure between 2.5 bar absolute and 4 bar absolute.
- the raw gas 3 is separated in the decomposition part 4 in the individual components.
- hydrogen H2, methane CH4, C2H4 ethylene, propylene, C3H6, a C 4+ fraction are recovered C4 + as well as other components. 5
- the C4 + fraction C4 + C5 + is 5+ fraction separated into a C 4 fraction and a C C4.
- the C 4 fraction is fed as an insert to a butadiene extraction 6 to form butadiene.
- the formed butadiene 8 is recovered as a product of value, while the residual C 4 fraction is recycled to the cracking furnace 2 C4R.
- the C 5+ fraction C5 + is also fed into a typical gasoline processing 7 with selective catalytic hydrogenations and aromatics extraction.
- the remaining C 5-8 fraction C5R is recycled to the cracking furnace 2.
- both the recycled, liquid C 4 fraction C4R and the recycled liquid C 5-8 fraction C5R are mixed with the liquid hydrocarbon-containing feed before it evaporates, mixed with water vapor and into the radiation zone and the Canned tubes is guided.
- the recycle and product quantities were determined in model calculations of Erfinderlnnen starting from a naphtha.
- fresh-naphtha cracking furnaces together with the C 4 cycle (C4R) and the C 5-8 cycle (C5R) and a furnace for the separate splitting of the ethane and propane recycle (not in FIG. 1 shown).
- the recycled amount of ethane and propane for the separate furnace, not shown, is reported in the table as a C 2 C 3 cycle.
- the results of a standardized plant balance and the process conditions at the furnaces for the cracking of the fresh naphtha with the C 4 cycle (C4R) and the C 5-8 cycle (C5R) are shown in Table 1.
- the amount of naphtha used was normalized as 100%.
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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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2012/003300 WO2013020676A1 (fr) | 2011-08-11 | 2012-08-02 | Procédé de dissociation d'hydrocarbures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201110110000 DE102011110000A1 (de) | 2011-08-11 | 2011-08-11 | Verfahren zur Spaltung von Kohlenwasserstoffen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2557142A1 true EP2557142A1 (fr) | 2013-02-13 |
Family
ID=45346146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11009116A Withdrawn EP2557142A1 (fr) | 2011-08-11 | 2011-11-17 | Procédé de craquage d'hydrocarbures |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2557142A1 (fr) |
DE (1) | DE102011110000A1 (fr) |
TW (1) | TW201313675A (fr) |
WO (1) | WO2013020676A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2867339B1 (fr) | 2012-08-09 | 2015-10-28 | Linde Aktiengesellschaft | Procédé de fabrication d'oléfines par vapocraquage thermique |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103275747B (zh) * | 2013-05-22 | 2014-12-31 | 中国石油天然气股份有限公司吉林石化分公司 | 乙烯装置裂解炉燃料气负荷分配方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1149360A (en) * | 1965-12-10 | 1969-04-23 | Hoechst Ag | Process for the manufacture of ethylene |
-
2011
- 2011-08-11 DE DE201110110000 patent/DE102011110000A1/de not_active Withdrawn
- 2011-11-17 EP EP11009116A patent/EP2557142A1/fr not_active Withdrawn
-
2012
- 2012-08-02 WO PCT/EP2012/003300 patent/WO2013020676A1/fr active Application Filing
- 2012-08-10 TW TW101129099A patent/TW201313675A/zh unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1149360A (en) * | 1965-12-10 | 1969-04-23 | Hoechst Ag | Process for the manufacture of ethylene |
Non-Patent Citations (2)
Title |
---|
P. ZAMOSTNY, Z. BELOHLAV: "A Rigorous Model of Ethylene Pyrolysis and its Applications", PETROLEUM AND COAL, vol. 45, no. 2-3, 1 January 2003 (2003-01-01), pages 142 - 146, XP002667965 * |
Z. BELOHLAV, P. ZAMOSTNY, T. HERINK: "The kinetic model of thermal cracking for olefins production", CHEMICAL ENGINEERING AND PROCESSING, vol. 42, 21 September 2002 (2002-09-21), pages 461 - 473, XP002667966 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2867339B1 (fr) | 2012-08-09 | 2015-10-28 | Linde Aktiengesellschaft | Procédé de fabrication d'oléfines par vapocraquage thermique |
Also Published As
Publication number | Publication date |
---|---|
DE102011110000A1 (de) | 2013-02-14 |
TW201313675A (zh) | 2013-04-01 |
WO2013020676A1 (fr) | 2013-02-14 |
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