EP1578891B1 - Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues - Google Patents

Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues Download PDF

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Publication number
EP1578891B1
EP1578891B1 EP02791874.7A EP02791874A EP1578891B1 EP 1578891 B1 EP1578891 B1 EP 1578891B1 EP 02791874 A EP02791874 A EP 02791874A EP 1578891 B1 EP1578891 B1 EP 1578891B1
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EP
European Patent Office
Prior art keywords
process according
deasphalting
catalyst
hydro
distillation
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EP02791874.7A
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German (de)
English (en)
French (fr)
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EP1578891A1 (en
Inventor
Alberto Delbianco
Nicoletta Panariti
Sebastiano Correra
Romolo Montanari
Sergio Rosi
Mario Marchionna
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Eni SpA
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Eni SpA
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting

Definitions

  • the present invention relates to a process for the conversion of heavy feedstocks, among which heavy crude oils, tars from oil sands and distillation residues, by the use of three process units: hydroconversion of the feedstock using catalysts in dispersed phase, distillation and deasphalting, suitably connected and fed with mixed streams consisting of fresh charge and conversion products.
  • the conversion of heavy crude oils, tars from oil sands and oil residues in liquid products can be substantially effected in two ways: one exclusively thermal, the other by means of hydrogenating treatment.
  • Hydrogenating processes consist in treating the charge in the presence of hydrogen and suitable catalysts.
  • Hydroconversion technologies currently on the market use fixed bed or ebullated bed reactors and catalysts generally consisting of one or more transition metals (Mo, W, Ni, Co, etc.) supported on silica/alumina (or equivalent material).
  • transition metals Mo, W, Ni, Co, etc.
  • Hydro-treatment technologies operating with catalysts in dispersed phase can provide an attractive solution to the drawbacks met in the use of fixed or ebullated bed technologies.
  • Slurry processes in fact, combine the advantage of a wide flexibility of the charge with high performances in terms of conversion and upgrading, and are therefore, in principle, simpler from a technological point of view.
  • Slurry technologies are characterized by the presence of particles of catalyst having very small average dimensions and effectively dispersed in the medium: for this reason hydrogenation processes are easier and more immediate in all points of the reactor. The formation of coke is considerably reduced and the upgrading of the charge is high.
  • the catalyst can be charged as powder with sufficiently reduced dimensions ( U.S. 4,303,634 ) or as oil-soluble precursor ( U.S. 5,288,681 ).
  • the active form of the catalyst generally the metal sulfide
  • the active form of the catalyst is formed in-situ by thermal decomposition of the compound used, during the reaction itself or after suitable pretreatment ( U.S. 4,470,295 ).
  • the metallic constituents of the dispersed catalysts are generally one or more transition metals (preferably Mo, W, Ni, Co or Ru). Molybdenum and tungsten have much more satisfactory performances than nickel, cobalt or ruthenium and even more than vanadium and iron ( N. Panariti et al., Appl. Catal. A: Jan. 2000, 204, 203 ).
  • the catalyst can be used at a low concentration (a few hundreds of ppm) in a "once-through" configuration, but in this case the upgrading of the reaction products is generally insufficient ( N. Panariti et al., Appl. Catal. A: Jan. 2000, 204, 203 and 215 ).
  • extremely active catalysts for example molybdenum
  • concentrations of catalyst for example molybdenum
  • the catalyst leaving the reactor can be recovered by separation from the product obtained from hydro-treatment (preferably from the bottom of the distillation column, downstream of the reactor) using conventional methods such as, for example, decanting, centrifugation or filtration ( U.S. 3,240,718 ; U.S. 4,762,812 ). Part of the catalyst can be recycled to the hydrogenation process without further treatment.
  • the catalyst recovered using known hydro-treatment processes normally has a reduced activity with respect to fresh catalyst and a suitable regeneration step must therefore be effected to restore the catalytic activity and recycle at least part of the catalyst to the hydro-treatment reactor.
  • Hydrocarbons which can be precipitated by a crude oil or oil residue by treatment with n-heptane under standard conditions established by regulation IP-143, are conventionally defined as asphaltenes.
  • phase separation phenomenon can be explained by the fact that as the conversion reactions proceed, the asphaltene phase becomes more and more aromatic due to dealkylation and condensation reactions.
  • the stability loss control of a heavy charge during a thermal and/or catalytic conversion process is therefore fundamental for obtaining the maximum conversion degree without running into problems relating to the formation of coke and fouling.
  • the optimum operating conditions (mainly reaction temperature and residence time) are simply determined on the basis of the stability data of the reactor effluent by means of direct measurements on the non-converted residue (P value, Hot Filtration Test, Spot Test, etc.).
  • This process comprises the following steps:
  • US 3,723,294 discloses a combination process for effecting a conversion of asphaltene-containing hydrocarbonaceous feedstock which is more efficient and which has the purpose of increasing catalyst life.
  • the process comprises the following steps:
  • hydroconversion with catalysts in slurry phase (HT), distillation or flash (D), deasphalting (SDA), is characterized in that the three units operate on mixed streams consisting of fresh charge and recycled streams, using the following steps:
  • the possible remaining part of the distillation residue (tar) or liquid leaving the flash unit, not recycled to the deasphalting zone, can be either totally or partially recycled, to the hydro-treatment section.
  • the catalysts can be selected from those obtained from easily decomposable oil-soluble precursors (metallic naphthenates, metallic derivatives of phosphonic acids, metal-carbonyls, etc.) or from preformed compounds based on one or more transition metals such as Ni, Co, Ru, W and Mo: the latter is preferred due to its high catalytic activity.
  • the concentration of catalyst defined on the basis of the concentration of metal or metals present in the hydroconversion reactor, ranges from 350 to 10000 ppm, preferably from 1000 to 8000 ppm, more preferably from 1500 to 5000 ppm.
  • the hydro-treatment step is preferably carried out at a temperature ranging from 370 to 480°C, preferably from 380 to 440°C, and at a pressure ranging from 3 to 30 MPa, preferably from 10 to 20 MPa.
  • the hydrogen is fed to the reactor, which can operate either under down-flow or, preferably up-flow conditions.
  • the gas can be fed to different sections of the reactor.
  • the distillation step is preferably carried out at reduced pressure, at a pressure ranging from 0.001 to 0.5 MPa, preferably from 0.05 to 0.3 MPa.
  • the hydro-treatment step can consist of one or more reactors operating within the range of conditions indicated above. Part of the distillates produced in the first reactor can be recycled to the subsequent reactors.
  • the deasphalting step effected by an extraction with a solvent, which may or may not be hydrocarbon, (for example with paraffins having from 3 to 6 carbon atoms), is generally carried out at temperatures ranging from 40 to 200°C and at a pressure ranging from 0.1 to 7 MPa. It can also consist of one or more sections operating with the same solvent or with different solvents; the solvent can be recovered under supercritical conditions thus allowing further fractionation between asphalt and resins.
  • a solvent which may or may not be hydrocarbon, (for example with paraffins having from 3 to 6 carbon atoms)
  • the stream consisting of deasphalted oil (DAO) can be used as such as synthetic crude oil (syncrude), optionally mixed with the distillates, or it can be used as feedstock for fluid bed Catalytic Cracking treatment or Hydrocracking.
  • DAO deasphalted oil
  • the fractions of fresh feedstock to be fed to the deasphalting and hydro-treatment sections can be modulated in the best possible way.
  • the process can be further improved, as far as the compatibility of the streams to be mixed is concerned, by controlling that the recycling between the streams containing asphaltenes, or fresh feedstock, tar and asphalt, has such a ratio that: ⁇ mix / RT ⁇ asph ⁇ ⁇ mix 2 ⁇ k wherein:
  • the asphaltenes used as reference for determining the properties indicated above are the insoluble n-heptane fraction (C 7 asphaltenes).
  • the application described is particularly suitable when the heavy fractions of complex hydrocarbon mixtures produced by the process must be used as feedstock for catalytic cracking plants, both Hydrocracking (HC) and fluid bed Catalytic Cracking (FCC).
  • HC Hydrocracking
  • FCC fluid bed Catalytic Cracking
  • HT catalytic hydrogenation unit
  • SDA extractive process
  • the investment cost of the whole complex can also be minimized as, with respect to the scheme described in patent application IT-95A001095 , for the same charge unit treated, the dimensions of the deasphalting section are increased whereas those of the hydro-treatment section (and downstream distillation column) are reduced; as the deasphalting unit involves lower investment costs than the hydro-treatment unit, there is a consequent saving on the investment cost of the whole complex.
  • a preferred embodiment of the present invention is now provided with the help of figure 1 enclosed, which however should not be considered as limiting the scope of the invention itself.
  • a part (1a) of the heavy feedstock (1) is sent to the deasphalting unit (SDA), an operation which is effected by means of extraction with solvent.
  • SDA deasphalting unit
  • SDA deasphalting unit
  • DAO deasphalted oil
  • asphalts and resins (3) the latter can be further separated into the two groups of compounds of which it is formed, and the fraction of resins (4) can be divided between DAO and asphalt.
  • the stream consisting of asphalt and resins (or a fraction of these) is mixed with fresh make-up catalyst (5) necessary for reintegrating that used up with the flushing stream (14), with the part of heavy feedstock (1b) not fed to the deasphalting section and optionally with the stream (15) (which will be described further on in the text) coming from the bottom of the distillation column (D) to form a stream (6) which is fed to the hydro-treatment reactor (HT) into which hydrogen (or a mixture of hydrogen and H 2 S) (7), is charged.
  • HT hydro-treatment reactor
  • a stream (8) containing the hydrogenation product and catalyst in dispersed phase leaves the reactor and is fractionated in a distillation column (D) from which the lighter fractions (9) and distillable products (10), (11) and (12) are separated from the distillation residue containing the dispersed catalyst and coke.
  • This stream, called tar, (13) is completely or for the most part, except for a flushing (14), recycled to the deasphalting reactor (SDA).
  • SDA deasphalting reactor
  • a part of this (15) can be optionally sent to the hydro-treatment unit (HT).
  • the asphaltene stream recovered at the end of the test contains all the catalyst initially fed, sulfides of the metals Ni and V produced during the 10 recycles from the hydro-treatment and a quantity of coke in the order of about 1% by weight with respect to the total quantity of Ural residue fed. In the example indicated, there was no need to effect any flushing of the recycled stream.
  • Table 2 provides the characterization of the product obtained. Table 2 : characteristics of test reaction products according to Example 1. Sulfur w% Nitrogen (ppm) Sp.Gr.
  • Table 3 provides the characterization of the product obtained.
  • Table 3 characteristics of test reaction products according to Example 2. Sulfur w% Nitrogen (ppm) Sp.Gr. RCC (w%) Ni+V (ppm) Naphtha C 5 -170°C 0.05 300 0.759 - - AGO 170-350°C 0.51 1950 0.864 - - VGO+DAO 1.45 2200 0.922 2.5 1
  • the following example shows the use of the relation ⁇ mix / RT ⁇ asph ⁇ ⁇ mix 2 ⁇ k indicated to evaluate the compatibility limits of the various streams to be subjected to hydro-treatment.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Working-Up Tar And Pitch (AREA)
EP02791874.7A 2002-12-30 2002-12-30 Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues Expired - Lifetime EP1578891B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2002/014847 WO2004058922A1 (en) 2002-12-30 2002-12-30 Process for the conversion of heavy charges such as heavy crude oils and distillation residues

Publications (2)

Publication Number Publication Date
EP1578891A1 EP1578891A1 (en) 2005-09-28
EP1578891B1 true EP1578891B1 (en) 2018-04-25

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EP02791874.7A Expired - Lifetime EP1578891B1 (en) 2002-12-30 2002-12-30 Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues

Country Status (7)

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EP (1) EP1578891B1 (no)
JP (1) JP4498929B2 (no)
AU (1) AU2002358182B8 (no)
EC (1) ECSP055872A (no)
ES (1) ES2679629T3 (no)
NO (1) NO20052951L (no)
WO (1) WO2004058922A1 (no)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20042445A1 (it) * 2004-12-22 2005-03-22 Eni Spa Procedimento per la conversione di cariche pesanti quali greggi pesanti e residui di distillazione
US9284499B2 (en) 2009-06-30 2016-03-15 Uop Llc Process and apparatus for integrating slurry hydrocracking and deasphalting
US8193401B2 (en) 2009-12-11 2012-06-05 Uop Llc Composition of hydrocarbon fuel
US8133446B2 (en) 2009-12-11 2012-03-13 Uop Llc Apparatus for producing hydrocarbon fuel
US9074143B2 (en) 2009-12-11 2015-07-07 Uop Llc Process for producing hydrocarbon fuel
CN103773433B (zh) * 2012-10-23 2016-12-21 中国石油天然气股份有限公司 一种劣质油品加氢处理方法

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US3723294A (en) * 1971-10-18 1973-03-27 Universal Oil Prod Co Conversion of asphaltene-containing hydrocarbonaceous charge stocks
NL7510465A (nl) * 1975-09-05 1977-03-08 Shell Int Research Werkwijze voor het omzetten van koolwaterstoffen.
NL8201119A (nl) * 1982-03-18 1983-10-17 Shell Int Research Werkwijze voor de bereiding van koolwaterstofoliedestillaten.
US4686028A (en) * 1985-04-05 1987-08-11 Driesen Roger P Van Upgrading of high boiling hydrocarbons
US5242578A (en) * 1989-07-18 1993-09-07 Amoco Corporation Means for and methods of deasphalting low sulfur and hydrotreated resids
IT1275447B (it) * 1995-05-26 1997-08-07 Snam Progetti Procedimento per la conversione di greggi pesanti e residui di distillazione a distillati
JP2003523451A (ja) * 2000-02-15 2003-08-05 エクソンモービル リサーチ アンド エンジニアリング カンパニー 溶剤脱歴と、それに続く溶剤脱歴からのアスファルトのスラリー水素処理に基づく重質原料の品質向上

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Publication number Publication date
AU2002358182A1 (en) 2004-07-22
NO20052951L (no) 2005-09-30
JP2006510781A (ja) 2006-03-30
WO2004058922A1 (en) 2004-07-15
AU2002358182A8 (en) 2004-07-22
ECSP055872A (es) 2005-09-20
NO20052951D0 (no) 2005-06-16
AU2002358182B2 (en) 2009-04-02
EP1578891A1 (en) 2005-09-28
ES2679629T3 (es) 2018-08-29
AU2002358182B8 (en) 2009-04-23
JP4498929B2 (ja) 2010-07-07

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