EP0009236B1 - Procédé de craquage d'hydrocarbures - Google Patents

Procédé de craquage d'hydrocarbures Download PDF

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Publication number
EP0009236B1
EP0009236B1 EP79103509A EP79103509A EP0009236B1 EP 0009236 B1 EP0009236 B1 EP 0009236B1 EP 79103509 A EP79103509 A EP 79103509A EP 79103509 A EP79103509 A EP 79103509A EP 0009236 B1 EP0009236 B1 EP 0009236B1
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EP
European Patent Office
Prior art keywords
fraction
hydrogen
residue
hydrogenation
gas
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Expired
Application number
EP79103509A
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German (de)
English (en)
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EP0009236A1 (fr
Inventor
Armin Dorner
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Linde GmbH
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Linde GmbH
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Priority to AT79103509T priority Critical patent/ATE702T1/de
Publication of EP0009236A1 publication Critical patent/EP0009236A1/fr
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence 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
    • 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 splitting hydrocarbons, in which the hydrocarbons are first hydrogenated and then thermally split.
  • light hydrocarbons such as ethane or propane or hydrocarbon mixtures with a boiling point below 200 ° C., for example naphtha, are particularly suitable as inserts for thermal cracking. They lead to a high yield and result in few undesirable by-products.
  • higher-boiling inserts basically has the problem that the olefin yield decreases and liquid fission products occur, the proportion of which increases sharply with the boiling range of the insert.
  • the liquid cleavage products are generally separated into a fraction boiling below 200 ° C. and a fraction boiling above 200 ° C.
  • the lower-boiling fraction is a high-octane fuel and contains valuable components such as benzene, toluene and xylene.
  • the fraction boiling above 200 ° C forms an undesirable product that contains highly condensed aromatics, polymeric compounds and sulfur compounds.
  • the fraction of this fraction, hereinafter referred to as residue, in the cleavage of naphtha is in the range from about 1 to 5% by weight of the total products and increases when using gas oil in the order of 30% by weight and for even heavier uses such as vacuum gas oil or Crude oil or crude oil residues to even higher values.
  • the sulfur contained in the feed material accumulates in the residue in such quantities that the combustion of this fuel without the addition of low-sulfur fuels leads to an unacceptably heavily polluted exhaust gas. Mixing with low-sulfur fuels is associated with further problems, however, because the residue is only miscible with crude oil distillates and can therefore only be partially blended with them. Another undesirable property of this fraction is that it can only be stored and transported to a limited extent.
  • FR-A-1 318 919 a process for the hydroconversion of hydrocarbons is known, the overall course of which also involves thermal fission.
  • thermal cracking residue without mentioning any details, it is only mentioned that it can be used as fuel or for the production of hydrogen.
  • US-A-3380910 a method is known, according to which a heavy crude oil distillate is prepared by hydrocracking and a light distillate by hydrodesulfurization. From this process, which does not provide for thermal cleavage, it is known to work up a heavy residue liquid, separated by distillation from a hydrocracking product, by partial oxidation to hydrogen. However, this process does not provide any indications of the favorable design of a process for the production of olefins.
  • the invention has for its object to design a method of the type mentioned in such a way that no products are obtained whose boiling range is above that of gasoline.
  • This object is achieved in that at least part of the residue of the thermal cleavage is converted into a gas mixture by partial oxidation.
  • a gas mixture consisting essentially of carbon oxides and hydrogen is generated from the residue fraction, which - optionally after cleaning and / or Disassembly into its individual components - can be used for a number of different processes, for example as a reducing gas, synthesis gas or heating gas.
  • the low-valued residue of the thermal fission is thus used to produce a gas mixture that can be used in a variety of ways and is economically interesting.
  • the partial oxidation can be carried out with air, with oxygen or with other oxygen-enriched gases or gas mixtures.
  • residue fraction freed from the polymeric compounds is reintroduced into the hydrogenation stage, particularly high yields can be achieved with regard to the desired process products, because the purified residue fraction in the hydrogenation and subsequent thermal cleavage gives products similar to the fresh feed.
  • Hydrogen is required for the reactions taking place in the hydrogenation stage.
  • the hydrogen generated during thermal cracking can be used directly after it has been separated from the other cracked products. In this way, however, only about 10 to 30% of the hydrogen requirement can generally be met.
  • a hydrogen-rich fraction is therefore separated from the gas mixture formed in the partial oxidation in a further embodiment of the invention and fed to the hydrogenation. With such a procedure, the hydrogen requirement to be covered by an external supply is particularly low.
  • part of the gas mixture can be recycled in the process itself, so that no precautions are required for the export of gas to separate plants.
  • the residual gas resulting from the separation of the gas mixture can be used, for example, as heating gas.
  • the hydrogenation product is a liquid fraction of hydrocarbons and a gaseous fraction which consists essentially of hydrogen and also contains light hydrocarbons and gaseous impurities such as hydrogen sulfide. While the light hydrocarbons from the gaseous fraction represent a favorable application for the thermal cracking, the excess hydrogen is returned to the hydrogenation stage after it has been separated off on a recycle base. For this procedure, a gas separation is required, in which the hydrogen and the impurities are separated from the light hydrocarbons.
  • the gas mixture obtained in the partial oxidation also has to be subjected to decomposition in order to separate the hydrogen for the hydrogenation, it is advantageous in a further development of the process according to the invention to digest this gas mixture together with the gaseous fraction obtained after the hydrogenation in order to reduce the costs for investment and operation of a process:; lower the plant accordingly.
  • the feed material for example a vacuum distillate, is fed to a hydrogenation stage 2 via line 1.
  • the hydrogenation can be carried out using conventional sulfur-resistant catalysts with elements of VI-VIII. Subgroup of the periodic table or mixtures thereof in elemental, oxidic or sulfidic form on a support made of silica, silica / alumina or on a zeolite basis.
  • Favorable hydrogenation conditions are present when a pressure between 10 and 300 bar, preferably between 15 and 150 bar, at temperatures between 100 and 500 ° C, preferably between 200 and 400 ° C, and at an hourly space velocity between 0.2 and 10 LI / h is worked.
  • the hydrogen required for the hydrogenation is fed to the hydrogenation stage 2 via line 3.
  • the hydrogenation product passes via line 4 to the expansion valve 29, in which it is expanded to the pressure of the thermal cleavage, preferably to a pressure between 1 and 4 bar.
  • the hydrogenation product then flows into a separator 5, where it is broken down into a gaseous fraction consisting essentially of hydrogen and into a liquid hydrogenation product.
  • the liquid fraction reaches a fractionation device 6, in which a heavy residue is separated from the hydrogenation product and drawn off via line 7 is withdrawn via line 8 while a lighter fraction boiling in the gasoline range is withdrawn.
  • This fraction reaches the thermal cracking stage 9 and is split there into an olefin-rich gas mixture.
  • the cleavage is advantageously carried out in a tube furnace at temperatures between 700 and 1000 ° C., a residence time between 0.01 and 1 sec and a steam dilution of 0.2 to 4.0 kg of water vapor per kg of hydrocarbons.
  • the hot cracked gas is then cooled and fed to a decomposition unit 10.
  • the individual fission products are isolated and drawn off separately from one another, which is indicated by the lines 11, 12, 13.
  • the pyrolysis residue which boils over 200 ° C. during the disassembly is drawn off via line 14 and fed into a device 15.
  • the residues from lines 7 and 14 are converted into a hydrogen-rich gas mixture by means of partial oxidation.
  • Water vapor is supplied via line 16 and air or oxygen via line 17 as the gasifying agent.
  • the raw gas formed in the partial oxidation is withdrawn via line 18. It consists essentially of hydrogen and carbon monoxide if oxygen is supplied via line 17, or of hydrogen, carbon monoxide and nitrogen if air is used as the gasifying agent via line 17.
  • the raw gas also contains impurities, especially hydrogen sulfide. The gas is therefore subjected to desulfurization 19, the separated hydrogen sulfide being removed via line 30.
  • the desulfurized gas is then fed via line 20 to a separation unit 21, in which the hydrogen is separated off.
  • the decomposition unit 21 can be, for example, a pressure swing adsorption system working with molecular sieves.
  • the separated hydrogen is withdrawn via line 3 and returned to the hydrogenation stage 2.
  • further hydrogen is supplied via line 22, which may at least partially come from the decomposition stage 10.
  • the residual gas consisting essentially of carbon monoxide or, in the case of partial oxidation with air, of carbon monoxide and nitrogen is withdrawn via line 23.
  • the gaseous fraction obtained in the separator 5 consists essentially of excess hydrogen from the hydrogenation 2 and, in addition, also contains light hydrocarbons which have formed during the hydrogenation, and also impurities, in particular hydrogen sulfide.
  • This fraction is fed via line 24 into a purification stage 25, in which the light hydrocarbons are separated off and fed to the thermal cracking 9 via line 26.
  • hydrogen sulfide is separated off in this purification stage and drawn off via line 27.
  • the cleaned gas is then introduced via line 28 into the cleaning stage 21, where it is subjected to a further cleaning together with the gas mixture supplied via line 20.
  • the method shown in FIG. 2 differs from that of FIG. 1 in three points.
  • the first difference is that the liquid hydrogenation product obtained in the separator 5 is not disassembled, but is led completely into the thermal cleavage 8 via line 31.
  • the second difference from the method in FIG. 1 is that the residue fraction which accumulates in the decomposition unit 10 and boils above 200 ° C. is not completely fed to the partial oxidation 15. Instead, this fraction drawn off via line 32 is fed into a treatment unit 33, in which the polymeric constituents of the fraction are separated off, for example by solvent extraction. The polymer-free fraction is withdrawn via line 34 and returned to the hydrogenation 2 together with fresh feed. The polymeric constituents of the heavy fraction are drawn off via line 35 and fed to the partial oxidation 15.
  • the third difference from the method in FIG. 1 consists in the joint processing of the gas obtained in the partial oxidation and the gaseous fraction from the separator 5 in a cleaning unit 36.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (5)

1. Procédé de craquage d'hydrocarbures selon lequel les hydrocarbures subissent tout d'abord une hydrogénation puis ensuite un craquage thermique, caractérisé en ce qu'au moins une partie du résidu du craquage thermique est transformée par oxydation partielle en un mélange gazeux.
2. Procédé selon la revendication 1, caractérisé en ce que l'oxydation partielle est effectuée en présence de vapeur d'eau.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il comprend une séparation des constituants polymères du résidu du craquage thermique, en ce que les constituants polymères sont transférés dans le mélange gazeux et en ce que les constituants restants du résidu du craquage thermique sont à nouveau soumis à l'hydrogénation.
4. Procédé selon une quelconque des revendications 1 à 3, caractérisé en ce que l'on sépare du mélange gazeux une fraction riche en hydrogène puis soumet cette fraction à l'hydrogénation.
5. Procédé selon la revendication 4, caractérisé en ce que le produit résultant de l'hydrogénation est séparé en une phase liquide et une phase gazeuse, en ce que l'on sépare de la phase gazeuse une fraction riche en hydrogène et une fraction riche en hydrocarbure, en ce que l'on conduit la fraction riche en hydrogène à l'hydrogénation et la fraction riche en hydrocarbure au craquage thermique et en ce que le mélange gazeux et la fraction gazeuse du produit résultant de l'hydrogénation sont fractionnés simultanément.
EP79103509A 1978-09-21 1979-09-19 Procédé de craquage d'hydrocarbures Expired EP0009236B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79103509T ATE702T1 (de) 1978-09-21 1979-09-19 Verfahren zum spalten von kohlenwasserstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782840987 DE2840987A1 (de) 1978-09-21 1978-09-21 Verfahren zum spalten von kohlenwasserstoffen
DE2840987 1978-09-21

Publications (2)

Publication Number Publication Date
EP0009236A1 EP0009236A1 (fr) 1980-04-02
EP0009236B1 true EP0009236B1 (fr) 1982-02-17

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EP79103509A Expired EP0009236B1 (fr) 1978-09-21 1979-09-19 Procédé de craquage d'hydrocarbures

Country Status (5)

Country Link
US (1) US4309271A (fr)
EP (1) EP0009236B1 (fr)
JP (1) JPS5543184A (fr)
AT (1) ATE702T1 (fr)
DE (2) DE2840987A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS585393A (ja) * 1981-07-01 1983-01-12 Asahi Chem Ind Co Ltd 重質油の熱分解方法
JPS588786A (ja) * 1981-07-10 1983-01-18 Mitsubishi Oil Co Ltd 炭素繊維原料用ピツチの製造方法
DE4328188C2 (de) * 1993-08-21 1996-04-18 Hoechst Ag Verfahren zur Herstellung von Synthesegas
US8709233B2 (en) 2006-08-31 2014-04-29 Exxonmobil Chemical Patents Inc. Disposition of steam cracked tar
US8083931B2 (en) * 2006-08-31 2011-12-27 Exxonmobil Chemical Patents Inc. Upgrading of tar using POX/coker
US8083930B2 (en) * 2006-08-31 2011-12-27 Exxonmobil Chemical Patents Inc. VPS tar separation
US8882991B2 (en) * 2009-08-21 2014-11-11 Exxonmobil Chemical Patents Inc. Process and apparatus for cracking high boiling point hydrocarbon feedstock
US9296955B2 (en) * 2010-09-20 2016-03-29 Exxonmobil Chemical Patents Inc. Process and apparatus for co-production of olefins and electric power
US10689587B2 (en) * 2017-04-26 2020-06-23 Saudi Arabian Oil Company Systems and processes for conversion of crude oil
RU2701860C1 (ru) * 2019-03-19 2019-10-02 Общество с ограниченной ответственностью "Научно-производственное объединение ЭТН-Циклон" Способ пиролиза жидких и газообразных углеводородов и устройство для его осуществления

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1667628A1 (de) * 1967-12-22 1972-03-30 Metallgesellschaft Ag Verfahren zur thermisch-oxydierenden Spaltung von Kohlenwasserstoffen
DE2012529B2 (de) * 1970-03-17 1973-07-05 Verfahren zur herstellung von im wesentlichen aus wasserstoff und kohlenoxiden bestehenden gasen mit geringem methangehalt
DE2805179A1 (de) * 1977-02-11 1978-08-17 Inst Francais Du Petrol Verfahren zur dampf-crackung von schweren chargen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1318919A (fr) * 1962-03-07 1963-02-22 Texaco Development Corp Perfectionnements apportés aux procédés pour l'hydroconversion d'hydrocarbures
US3380910A (en) * 1966-05-17 1968-04-30 Chemical Construction Corp Production of synthetic crude oil
GB1361671A (en) * 1971-01-06 1974-07-30 Bp Chem Int Ltd Process for the production of gaseous olefins from petroleum distillate feedstocks
NL7507484A (nl) * 1975-06-23 1976-12-27 Shell Int Research Werkwijze voor het omzetten van koolwaterstoffen.
GB1504776A (en) * 1975-08-14 1978-03-22 Davy Powergas Ltd Hydrocracking c3 or higher hydrocarbon feedstock
US4115246A (en) * 1977-01-31 1978-09-19 Continental Oil Company Oil conversion process
FR2390493B1 (fr) * 1977-05-12 1985-04-26 Linde Ag Procede de preparation d'olefines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1667628A1 (de) * 1967-12-22 1972-03-30 Metallgesellschaft Ag Verfahren zur thermisch-oxydierenden Spaltung von Kohlenwasserstoffen
DE2012529B2 (de) * 1970-03-17 1973-07-05 Verfahren zur herstellung von im wesentlichen aus wasserstoff und kohlenoxiden bestehenden gasen mit geringem methangehalt
DE2805179A1 (de) * 1977-02-11 1978-08-17 Inst Francais Du Petrol Verfahren zur dampf-crackung von schweren chargen

Also Published As

Publication number Publication date
US4309271A (en) 1982-01-05
ATE702T1 (de) 1982-03-15
JPS5543184A (en) 1980-03-26
DE2840987A1 (de) 1980-04-03
DE2962149D1 (en) 1982-03-25
EP0009236A1 (fr) 1980-04-02

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