EP0555301B1 - Verfahren und anlage zur erzeugung von flüssigen kraftstoffen und chemierohstoffen - Google Patents

Verfahren und anlage zur erzeugung von flüssigen kraftstoffen und chemierohstoffen Download PDF

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Publication number
EP0555301B1
EP0555301B1 EP91918850A EP91918850A EP0555301B1 EP 0555301 B1 EP0555301 B1 EP 0555301B1 EP 91918850 A EP91918850 A EP 91918850A EP 91918850 A EP91918850 A EP 91918850A EP 0555301 B1 EP0555301 B1 EP 0555301B1
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EP
European Patent Office
Prior art keywords
cracking
installation
butane
isobutane
unit
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
EP91918850A
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German (de)
English (en)
French (fr)
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EP0555301A1 (de
Inventor
Simon Barendregt
Jean Lucien Monfils
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
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 Mannesmann AG, KTI Group BV filed Critical Mannesmann AG
Publication of EP0555301A1 publication Critical patent/EP0555301A1/de
Application granted granted Critical
Publication of EP0555301B1 publication Critical patent/EP0555301B1/de
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • 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
    • 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

Definitions

  • the invention relates to a method and a plant for the production of liquid fuels and chemical raw materials from petroleum in the context of a refinery process.
  • a refinery process usually consists of a combination of numerous physical and chemical sub-processes. Particularly noteworthy here are the processes for distillation (at different pressures), for catalytic reforming, for hydrorefining and for cracking higher hydrocarbons. In the following, the hydrocarbons are often shortened depending on the number of C atoms with C1, C2, C3, C4, C5+ (five and more C atoms).
  • Crude oil (CRUDE) is divided in a distillation unit (DEST) into a number of different fractions, which are usually not homogeneous substances but represent mixed products.
  • a relatively light fraction leaves the distillation unit as the top product and is separated into a gaseous and a liquid phase in a collecting container (ACCU).
  • the lightest components (C1, C2, H2S) are placed in a plant (ASR) in which they are freed of sulfur by amines.
  • the resulting products are a gas stream G and a volume stream (S) of sulfur.
  • the heavier components are given from the collection container (ACCU) in a naphtha hydrogenation treatment (VNHDT), but can also be marketed directly as chemical raw material (CF).
  • VNHDT naphtha hydrogenation treatment
  • CF chemical raw material
  • the naphtha hydrogenation treatment results in a salable naphtha (NA), which is further processed by a catalytic reforming treatment (CREF), in which in particular an H2-rich gas (H2R) and gasoline (Reformate REF, predominantly C5-C10) are produced can be.
  • CREF catalytic reforming treatment
  • VNHDT naphtha hydrogenation treatment
  • CREF catalytic reforming
  • LPG liquefied petroleum gas
  • VNHDT naphtha hydrogenation treatment
  • C5- Components C5- Components
  • VRU fractionation system
  • the remaining gaseous components in particular H2, CO, CO2, C1, C2 are added to the gas stream G already mentioned, while the other fractions (C3, C4, C5) in subordinate (parallel) process steps (AIDP), the one Alkylation, isomerization, dimerization and also polymerisation can be further processed to various gasoline products (GP).
  • the kerosene and diesel fractions separated in the distillation unit are each subjected to a desulfurization and hydrogenation treatment (HDS) and then represent salable products.
  • DEST distillation unit
  • HDS desulfurization and hydrogenation treatment
  • the lighter part of the heavy hydrocarbons is fed to a catalytic cracking unit (FCC), but can also be used as heavy fuel oil (FO).
  • the bottom product of the distillation unit (DEST) is also fed into the catalytic cracking unit (FCC) after passing through a vacuum distillation (VDEST). If necessary, the cracking can also be carried out with the addition of H2.
  • the resulting gaseous fraction (C1, C2, NH3, H2S) is fed into the ASR system, while the liquid gas components (C3, C4) are passed as LPG into the fractionation system (VRU). Any diesel components generated are added to the diesel power (DIE).
  • the main end product in the catalytic cracking plant (FCC) is a stream of high-quality motor gasoline (FCCG).
  • FCCG high-quality motor gasoline
  • the remaining heavy hydrocarbons are used as heavy heating oil (FO) as is the bottom product from vacuum distillation (VDEST), which can also be subjected to a thermal cracking process (VISBR).
  • FIG. 2 shows a similar refinery process which is also part of the prior art.
  • a catalytic cracker FCC
  • HYCR hydrocracker
  • VRU fractionation unit
  • C5+ gasoline products
  • the gasoline products produced in the refinery process still contain significant amounts of dissolved butane.
  • the content of the volatile butane in petrol to a comparatively low residual value.
  • the obvious use for the production of process steam is not always useful, because there is often no need for the additional steam generated. In addition, this is not desirable for economic reasons because the combustion destroys a relatively high-quality raw material.
  • butane It is generally known to process butane into usable products. These products include gasoline additives to increase the octane number, which are used as an alternative to the lead compounds previously used for this purpose. For environmental reasons, the use of lead compounds is increasingly restricted. Instead, substances such as MTBE (methyl tertiary butyl ether) and ETBE (ethyl tertiary butyl ether) are used, which are usually produced in separate large-scale plants. Butane is used as the starting material, the n-butane portion of which is first converted into isobutane and then converted into isobutylene. This implementation takes place in the form of a catalytic process. Thermal cracking of isobutane is also fundamentally known, in which in addition to isobutylene, proportions of propylene and ethylene in particular are formed which cannot be used for the production of MTBE or ETBE.
  • MTBE methyl tertiary butyl ether
  • ETBE ethyl tert
  • MTBE or ETBE takes place by reacting isobutylene with methanol or ethanol in the presence of acidic catalysts (e.g. ion exchangers).
  • acidic catalysts e.g. ion exchangers
  • the invention is based on the object of proposing a recycling option which is as favorable as possible in terms of the requirements of environmental protection in technical and economic terms.
  • FIGS. 1 to 3 showing conventional refinery processes with a fluid bed cracker (FCC) or with a hydrocracker (HYCR) and FIG. 3 showing a possible circuit diagram for supplementing the refinery process according to the invention.
  • FCC fluid bed cracker
  • HYCR hydrocracker
  • FIGS. 1 and 2 have already been explained in detail at the beginning, there is no need to go into this again.
  • the scheme of Figure 3 can follow these two refinery processes, for example.
  • the connection point between the individual figures can be seen in each case in the fractionation system (VRU), which in particular includes the various flows of the liquefied petroleum gas LPG produced in the refinery process.
  • VRU fractionation system
  • At least some of the C4 components which usually contain isobutylene in an order of magnitude of about 20% by weight, are led according to the invention as mass flow 5 together with a stream of methanol 6 into an MTBE plant for the production of methyl tertiary butyl ether.
  • the MTBE product stream generated is designated by 9.
  • ETBE can be produced in the same way by adding ethanol instead of methanol. Since only the isobutylene in the MTBE plant takes part in the conversion to MTBE, the proportion of the non-converted C4 components is subjected to a cracking treatment to produce isobutylene.
  • the stream 10 of the C4 components is first passed into a separation device SP, in which n-butane is separated from isobutane.
  • the n-butane is fed from the separating device SP into an isomerization ISO (line 11) and is returned from this to the separating device SP (line 12) to separate the isobutane.
  • the formation of isobutane is thus carried out in a secondary circuit in the case shown, so that the cracking plant CR, into which the isobutane passes via line 13, is not burdened with the proportion of the undesired n-butane. It is also possible to bypass part of the mass flow 5 in a bypass past the MTBE plant directly into the complex of the isomerization and isobutylene production.
  • the CR cracking system works according to the thermal cracking process. In the present case, this is significantly cheaper than a catalytic conversion, since a thermal cracker, in addition to isobutylene, in particular also produces considerable amounts of propylene, which is very desirable in the refinery process as a particularly high-quality salable product or for subsequent processing.
  • catatytic conversion of isobutane would only provide isobutylene in amounts such that its further processing into MTBE (or ETBE) or atylate gasoline would produce an unnecessarily large amount of the gasoline additive in relation to the amounts of the other gasoline products produced.
  • the isobutylene passes from the cracking plant CR with the unconverted proportion of isobutane via line 14 into the fractionation plant VRU. From there, the cycle of the unconverted C4 components can begin again via the MTBE production plant.
  • MTBE or ETBE production with an attached butane cracking plant enables the use of the butane quantities obtained in an optimal manner.
  • a particularly valuable gasoline additive (MTBE or ETBE) is produced which, due to the use of thermal cracking, which is unusual per se, provides the isobutylene in such quantities that it is possible to produce the quantity of gasoline additive adapted to the requirements of the gasoline product quantities. It is very important that a lot of economically particularly valuable propylene is formed in this process.
  • the refinery process as a whole can be operated with a balanced energy balance, so that neither imports nor exports of energy or process steam are required.
  • the mass flow 14 returned from the thermal cracking plant CR into the fractionation VRU had the following composition (% by weight): gas 0.86% Propylene 0.72% propane 0.04% Isobutylene 0.89% n-butylene - Isobutane 2.08% n-butane 0.01% C5+ 0.07% 4.67%
  • the process according to the invention thus made it possible to reduce the butane content in the end product from 1.87% by weight to only 0.39% by weight, that is to say to approximately 20% of the original value.
  • an amount of 1.49% by weight of valuable MTBE was produced as a gasoline additive, for which purpose only 0.54% by weight of methanol had to be added from the outside.
  • the amount of alkylates decreased relatively slightly by about 0.4% by weight, while the amount of C5+ products increased by about 0.1% by weight.
  • the increase in the amount of gas separated in the fractionation by approximately 0.9% by weight, that is to say by almost 60% of the original value, since this increase is essentially due to additionally produced high-quality propylene.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
EP91918850A 1990-11-02 1991-10-30 Verfahren und anlage zur erzeugung von flüssigen kraftstoffen und chemierohstoffen Expired - Lifetime EP0555301B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4035274A DE4035274C1 (enExample) 1990-11-02 1990-11-02
DE4035274 1990-11-02
PCT/DE1991/000851 WO1992007921A1 (de) 1990-11-02 1991-10-30 Verfahren und anlage zur erzeugung von flüssigen kraftstoffen und chemierohstoffen

Publications (2)

Publication Number Publication Date
EP0555301A1 EP0555301A1 (de) 1993-08-18
EP0555301B1 true EP0555301B1 (de) 1994-09-07

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EP91918850A Expired - Lifetime EP0555301B1 (de) 1990-11-02 1991-10-30 Verfahren und anlage zur erzeugung von flüssigen kraftstoffen und chemierohstoffen

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Country Link
US (1) US5670703A (enExample)
EP (1) EP0555301B1 (enExample)
JP (1) JPH06504072A (enExample)
KR (1) KR930702474A (enExample)
AT (1) ATE111148T1 (enExample)
CA (1) CA2095122A1 (enExample)
DE (2) DE4035274C1 (enExample)
MY (1) MY109761A (enExample)
WO (1) WO1992007921A1 (enExample)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5600024A (en) * 1995-07-26 1997-02-04 Phillips Petroleum Company Enhanced recovery of alcohol from an ether containing stream
WO2018185628A1 (en) 2017-04-03 2018-10-11 Sabic Global Technologies B.V. Systems and methods of producing methyl tertiary butyl ether and propylene
CA3069332C (en) 2017-07-18 2022-06-07 Lummus Technology Llc Integrated thermal and catalytic cracking for olefin production
CN111132956B (zh) 2017-07-19 2023-04-25 沙特基础工业全球技术公司 Mtbe萃余液在丙烯生产中的用途
US10995045B2 (en) * 2018-10-09 2021-05-04 Uop Llc Isomerization zone in alkylate complex

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2620356A1 (fr) * 1987-09-14 1989-03-17 Lesieur Bernard Appareillage pour l'application de traitements de surfaces a des structures allongees

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4569753A (en) * 1981-09-01 1986-02-11 Ashland Oil, Inc. Oil upgrading by thermal and catalytic cracking
FR2520356B1 (fr) * 1982-01-26 1987-09-18 Inst Francais Du Petrole Procede de valorisation des coupes c4 olefiniques
US4546204A (en) * 1983-11-07 1985-10-08 Imperial Chemical Industries Australia Limited Process for the manufacture of methyl t-butyl ether
US4581474A (en) * 1985-03-11 1986-04-08 Phillips Petroleum Company Hydrocarbon conversion process
US5001292A (en) * 1987-12-08 1991-03-19 Mobil Oil Corporation Ether and hydrocarbon production
GB8804033D0 (en) * 1988-02-22 1988-03-23 Shell Int Research Process for preparing normally liquid hydrocarbonaceous products from hydrocarbon feed
US5254748A (en) * 1990-09-04 1993-10-19 Phillips Petroleum Company Methyl-tertiary ether production
IT1247108B (it) * 1991-02-28 1994-12-12 Snam Progetti Procedimento integrato per la produzione di iso-butene ed eteri alchil-ter-butilici.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2620356A1 (fr) * 1987-09-14 1989-03-17 Lesieur Bernard Appareillage pour l'application de traitements de surfaces a des structures allongees

Also Published As

Publication number Publication date
DE4035274C1 (enExample) 1991-11-07
US5670703A (en) 1997-09-23
JPH06504072A (ja) 1994-05-12
KR930702474A (ko) 1993-09-09
CA2095122A1 (en) 1992-05-03
ATE111148T1 (de) 1994-09-15
WO1992007921A1 (de) 1992-05-14
MY109761A (en) 1997-06-30
DE59102871D1 (de) 1994-10-13
EP0555301A1 (de) 1993-08-18

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