EP0159867A2 - Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas - Google Patents

Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas Download PDF

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Publication number
EP0159867A2
EP0159867A2 EP85302550A EP85302550A EP0159867A2 EP 0159867 A2 EP0159867 A2 EP 0159867A2 EP 85302550 A EP85302550 A EP 85302550A EP 85302550 A EP85302550 A EP 85302550A EP 0159867 A2 EP0159867 A2 EP 0159867A2
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EP
European Patent Office
Prior art keywords
gas
process according
reactor
hydroconversion
hydrogen sulphide
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EP85302550A
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English (en)
French (fr)
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EP0159867A3 (en
EP0159867B1 (de
Inventor
Jörn Ehlers
Wilfried Johann Petzny
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BP PLC
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BP PLC
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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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/18—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide

Definitions

  • the invention relates to a process for the hydroconversion of sulphur-containing heavy hydrocarbons with synthesis gas in the presence of steam in which synthesis gas and the hydrocarbons are reacted in a reactor at elevated temperature and pressure.
  • Recycle gas from the hydroconversion reaction may be mixed with the synthesis gas.
  • GB 257 256 discloses the conversion of coal or mineral oils into valuable liquid products by the action of hydrogen and carbon monoxide. The possible presence of sulphur in the material to be treated and the recycle of unreacted synthesis gas is mentioned.
  • GB 400 844 and GB 407 127 disclose the hydrogenation of oil and coal/oil paste with hydrogen alone or with C0, H 2 S, steam.
  • DE 713 792 discloses the hydrogenation of wood tars.
  • the presence of 1-15% by weight (based on material to be hydrogenated) of H 2 S is said to improve the effectiveness of iron, cobalt and nickel catalysts.
  • DE 2 751 863 describes a two stage hydrotreatment for heavy hydrocarbons.
  • the first stage is preferably carried out in the presence of a quantity of H 2 S sufficient to ensure that the volume of this gas is more than 10% at the reactor outlet.
  • H 2 S a quantity of H 2 S sufficient to ensure that the volume of this gas is more than 10% at the reactor outlet.
  • synthesis gas in place of pure hydrogen.
  • Hettinger et al are concerned with the hydroforming of relatively low boiling hydrocarbons to give gasoline, and sulphur is stated to have an adverse effect on this reaction.
  • a process for the hydroconversion of sulphur containing heavy hydrocarbons in which (1) a gas containing carbon monoxide and steam, and (2) the hydrocarbons are converted in a reactor at elevated temperature and pressure is characterised in that the gas fed to the reactor comprises at least 3% by volume of hydrogen sulphide, based on water free gas.
  • the gas containing CO and steam used as a feed in the process of the present invention may be derived only from fresh synthesis gas with added steam or may also contain recycled unreacted gas.
  • the process of the present invention is preferably carried out continuously.
  • the hydrocarbons and the gas are heated in a pre-heating step before they are fed to the reactor.
  • the gas fed to the reactor comprises at least 5% by volume of H 2 S.
  • synthesis gas we mean a gas mixture principally of CO and H 2 obtained for example by gasification of fossil fuels such as lignite, crude oil, natural gas, coal, wood, heavy oil residues and the like or by steam cracking of normally gaseous or liquid light hydrocarbon fractions.
  • a typical synthesis gas for use in the process of the invention contains CO and H 2 in various ratios to each other as well as distinguishable quantities of steam and small quantities of C0 2 , COS and lower hydrocarbons. The latter originate in particular from the recycle gas.
  • Synthesis gas freed from hydrogen ie consisting mainly of CO can be used.
  • H 2 is present.
  • the process of the present invention may be applied to uncatalysed reactions e.g. hydrovis-breaking. However it is particularly useful to apply the process to reactions carried out in the presence of a catalyst. Thus the process may be applied to catalytic hydrocracking.
  • Catalysts which can be used in the process of the invention are known for example from the above mentioned GB 1072697 as well as from DE OS 32 12 389.
  • suitable catalysts are carbonaceous solids e.g. coal, coke or charcoal, which may be coated with up to 20% wt of a metal catalyst such as iron group metal (iron, nickel, cobalt), molybdenum, zinc, tin, tungsten, chromium.
  • the catalysts can be used in finely divided suspended form ("slurry phase"), as an ebulliated bed or as a solid bed.
  • the catalysts quantities employed in the "slurry phase” method are for example 0.2-5% by weight, calculated on the hydrocarbon feed.
  • the steam required for the reaction can be added together with the fresh feed gas, or fresh gas and recycle gas, or can be added separately.
  • the quantity of steam used will depend on the quantity of hydrogen fed to the reactor as it is believed that the water produces hydrogen by the shift reaction. An excessively high proportion of steam will reduce the partial pressure of the C0. The optimum quantity can be found by simple tests.
  • the quantity of steam may be defined by the amount of liquid water used to produce the steam. The optimum amount of liquid water will in general be within the range 10 to 1000 ml liquid water per kg of liquid hydrocarbon fed, for example 20-200 ml of water per kg of liquid hydrocarbon fed.
  • the reaction temperature is typically 300-500°C and the reaction pressure 1.5-30 MPa.
  • heavy hydrocarbons which can be used are for example atmospheric or vacuum residues from crude oil distillations as well as heavy hydrocarbons from tar sands and oil shales.
  • the hydrocarbon is introduced to the reactor with a LHSV rate of 0.2-10 1/1/h in continuous processes.
  • the ratio of gaseous feed to hydrocarbon is preferably in the range 500-5000 1/kg (litres gas at normal temperature and pressure (0°C, 0.1 MPa pressure) per kg of hydrocarbon).
  • this gaseous feed can consist of fresh synthesis gas only (and steam) or synthesis gas and recycle gas (and steam).
  • any recycled unreacted gas will be treated so as to remove impurities, and this will result in removal of most of any hydrogen sulphide present.
  • hydrogen sulphide In order to obtain the desired level of hydrogen sulphide in the feed to the reactor, hydrogen sulphide must be added.
  • the hydrogen sulphide may be hydrogen sulphide produced in the reactor from sulphur-containing compounds and which is recovered from the gas treatment step. Such recovered hydrogen sulphide may be added back to the recycle gas immediately after the gas treatment step, or may be added to the fresh gas feed, or to the mixture of fresh and recycle gas.
  • hydrogen sulphide which is not produced in the process, particularly on starting the plant or when using a feed with a relatively low sulphur content.
  • hydrogen sulphide can also be introduced from other sources e.g. from a Claus process.
  • Increasing hydrogen sulphide content in the reaction system can lower the partial pressure of hydrogen and carbon monoxide to such an extent that the degree of conversion of the heavy hydrocarbon declines; the practical upper limit for the hydrogen sulphide content in the system can however be determined easily by the person of ordinary skill for each individual case.
  • the H 2 S content of the feed gas preferably does not exceed 20% volume.
  • the apparatus comprises a hydrocracking reactor 1, which can consist of one or more similar reactors arranged in series, one or more hot separators 2 giving a first coarse separation of the hydrocracking product, one or more reactors 3 in which a post hydrogenation of unsaturated hydrocarbons takes place e.g. in a solid bed with Co/Mo or Ni/Mo-catalysts takes place, as well as a section 4 for gas and product separation in the form of for example a plurality of product separators working with or without pressure, and further apparatus for gas separation such as wash towers, membrane and/or low temperature separation stages.
  • a hydrocracking reactor 1 can consist of one or more similar reactors arranged in series, one or more hot separators 2 giving a first coarse separation of the hydrocracking product, one or more reactors 3 in which a post hydrogenation of unsaturated hydrocarbons takes place e.g. in a solid bed with Co/Mo or Ni/Mo-catalysts takes place, as well as a section
  • the reactor 1 is provided with a mixture of heavy hydrocarbons and catalyst through line 5.
  • line 5 there are one or more pumps and preheater stages 7.
  • Synthesis gas is led through line 8
  • H 2 S is led through line 9.
  • Steam is led through line 10 or 11 and recycled gas through line 12.
  • Unconverted or insufficiently converted hydrocarbon material separated in hot separator 2 is removed by line 13 or is partly recycled to the conversion reaction through line 14.
  • H 2 S and synthesis gas are taken off separately through lines 15 and optionally returned to the process.
  • Lines 16 serve for removal of C0 2 , C l -C 3 hydrocarbons as well as higher hydrocarbons.
  • the heavy liquid hydrocarbon feedstock used in these experiments was an atmospheric residue (derived from a Boscan crude) with the following characteristics: V 1900 ppm
  • the autoclave is pressurised to 80 bar (8 MPa)with hydrogenating gas, heated quickly to 440°C, maintained at this temperature for one hour, and then cooled down.
  • Comparative Test D shows that the use of mixtures of CO and H 2 S give very high coke yields. Such results would not encourage any one to believe that hydrogen sulphide was in any way satisfactory as a hydrogenating gas.
  • Comparative Test A shows that there has been a relatively small increase in hydrogen consumption.
  • the total amount of material boiling in the range C i -530°C is slightly lower when H 2 S is used while the amount of the less desirable high boiling material (boiling at temperatures above 530°C) is higher when H2 S is added.
  • the asphaltene content is also lower in the product obtained according to the invention, and the hydrogen content in the fraction boiling above 170°C is higher.

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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)
  • Hydrogen, Water And Hydrids (AREA)
EP19850302550 1984-04-13 1985-04-11 Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas Expired EP0159867B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3413987 1984-04-13
DE3413987 1984-04-13

Publications (3)

Publication Number Publication Date
EP0159867A2 true EP0159867A2 (de) 1985-10-30
EP0159867A3 EP0159867A3 (en) 1986-01-15
EP0159867B1 EP0159867B1 (de) 1988-01-27

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EP19850302550 Expired EP0159867B1 (de) 1984-04-13 1985-04-11 Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas

Country Status (4)

Country Link
EP (1) EP0159867B1 (de)
JP (1) JPS61501855A (de)
ES (1) ES8606465A1 (de)
WO (1) WO1985004670A2 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2791418B2 (ja) 1987-12-02 1998-08-27 株式会社ミドリ十字 異種蛋白質の製造方法、組換えｄｎａ、形質転換体
DK238288A (da) * 1988-05-03 1989-11-04 Maltarp As Cirkelringformet boerstesektion til fejemaskine og fremsgangsmaade til fremstilling af en saadan boerstesektion

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2054776A (en) * 1932-08-26 1936-09-15 Standard I G Company Ltd Conversion of carbonaceous materials
DE713792C (de) * 1930-04-06 1941-11-24 Degussa Verfahren zur Druckhydrierung von kohlenstoffhaltigen Stoffen
FR2371504A1 (fr) * 1976-11-22 1978-06-16 Shell Int Research Procede pour la preparation de distillats atmospheriques d'huiles d'hydrocarbures
GB2072697A (en) * 1980-03-26 1981-10-07 Ca Minister Energy Hydrocracking of heavy hydrocarbon using synthesis gas
DE3212389A1 (de) * 1981-04-08 1982-11-04 Deutsche Bp Ag, 2000 Hamburg Verfahren zur herstellung eines gemisches aus kohlestaemmigen materialien und katalysatoren zur verwendung in hydrierverfahren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE713792C (de) * 1930-04-06 1941-11-24 Degussa Verfahren zur Druckhydrierung von kohlenstoffhaltigen Stoffen
US2054776A (en) * 1932-08-26 1936-09-15 Standard I G Company Ltd Conversion of carbonaceous materials
FR2371504A1 (fr) * 1976-11-22 1978-06-16 Shell Int Research Procede pour la preparation de distillats atmospheriques d'huiles d'hydrocarbures
GB2072697A (en) * 1980-03-26 1981-10-07 Ca Minister Energy Hydrocracking of heavy hydrocarbon using synthesis gas
DE3212389A1 (de) * 1981-04-08 1982-11-04 Deutsche Bp Ag, 2000 Hamburg Verfahren zur herstellung eines gemisches aus kohlestaemmigen materialien und katalysatoren zur verwendung in hydrierverfahren

Also Published As

Publication number Publication date
ES8606465A1 (es) 1986-04-01
WO1985004670A2 (en) 1985-10-24
WO1985004670A3 (en) 1985-11-21
EP0159867A3 (en) 1986-01-15
JPS61501855A (ja) 1986-08-28
EP0159867B1 (de) 1988-01-27
ES542204A0 (es) 1986-04-01

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