EP0159867B1 - Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas - Google Patents

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

Info

Publication number
EP0159867B1
EP0159867B1 EP19850302550 EP85302550A EP0159867B1 EP 0159867 B1 EP0159867 B1 EP 0159867B1 EP 19850302550 EP19850302550 EP 19850302550 EP 85302550 A EP85302550 A EP 85302550A EP 0159867 B1 EP0159867 B1 EP 0159867B1
Authority
EP
European Patent Office
Prior art keywords
gas
process according
reactor
synthesis gas
hydroconversion
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
Application number
EP19850302550
Other languages
English (en)
French (fr)
Other versions
EP0159867A3 (en
EP0159867A2 (de
Inventor
Jörn Ehlers
Wilfried Johann Petzny
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.)
BP PLC
Original Assignee
BP PLC
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 BP PLC filed Critical BP PLC
Publication of EP0159867A2 publication Critical patent/EP0159867A2/de
Publication of EP0159867A3 publication Critical patent/EP0159867A3/en
Application granted granted Critical
Publication of EP0159867B1 publication Critical patent/EP0159867B1/de
Expired legal-status Critical Current

Links

Images

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
    • 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 CO, 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.
  • GB 2 072 697 discloses a heavy oil cracking process using synthesis gas (H 2 , CO).
  • the gas recovered from the cold separator contains H 2 , CO, C0 2 and some impurities e.g. H 2 S and light hydrocarbon gases.
  • H 2 S synthesis gas
  • GB 2 072 697 describes passing the recycled gas through a scrubbing system. This scrubbing process will remove materials such as carbon dioxide and hydrogen sulphide. The hydrogen sulphide concentration in the recycled gas will therefore be low.
  • hydrogen sulphide is stated to be an impurity and not a desirable constituent of the reaction mixture.
  • 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 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 i.e. 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 catalyst hydrocracking.
  • Catalysts which can be used in the process of the invention are known for eaxample from the above mentioned GB 1 072 697 as well as from DE OS 3 212 389.
  • 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 suspension 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 CO. 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 distillation 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 I/I/h in continuous processes.
  • the ratio of gaseous feed to hydrocarbon is preferably in the range 500-5000 I/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 4 for gas and product separation in the
  • 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 serves 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:
  • 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 anyone 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 H 2 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.

Landscapes

  • 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)

Claims (11)

1. Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen, bei dem (1) ein Carbonmonoxid und Wasserdampf enthaltendes Gas und (2) die Kohlenwasserstoffe in einem Reaktor bei erhöhter Temperatur und erhöhtem Druck umgewandelt werden, dadurch gekennzeichnet, dass das dem Reaktor zugeführte Gas wenigstens 3 Vol.-% Hydrogensulfid, bezogen auf das wasserfreie Gas, umfasst.
2. Verfahren nach Anspruch 1, worin das Verfahren kontinuierlich durchgeführt wird.
3. Verfahren nach Anspruch 2, worin das Gas und der Kohlenwasserstoff vor dem Einleiten in den Reaktor einem Schritt des Vorheizens unterworfen werden.
4. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das der Vorheizeinrichtung zugeführte Gas wenigstens 3 Vol. % H2S enthält.
5. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das Gas wenigstens 5 Vol.-% H2S enthält.
6. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das Gas Wasserstoff umfasst.
7. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das Gas H2S enthält, das nicht in dem Verfahren erzeugt worden ist.
8. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das Gas H2S enthält, das von dem Produkt-Gas abgetrennt worden ist.
9. Verfahren nach irgendeinem der vorhergehenden Anprüche, worin das Verfahren der Wasserstoffumwandlung in Gegenwart eines Katalysators stattfindet.
10. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin der Katalysator ein festes, kohlenstoffhaltiges Material und ein Metall der EisenGruppe umfasst.
11. Verfahren nach irgendeinem der vorhergehenden Ansprüche, worin das Verfahren in Gegenwart einer Dispersion eines Katalysators stattfindet.
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 EP0159867A2 (de) 1985-10-30
EP0159867A3 EP0159867A3 (en) 1986-01-15
EP0159867B1 true EP0159867B1 (de) 1988-01-27

Family

ID=6233500

Family Applications (1)

Application Number Title Priority Date Filing Date
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

Family Cites Families (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
NL35908C (de) * 1932-08-26
NL7612960A (nl) * 1976-11-22 1978-05-24 Shell Int Research Werkwijze voor het omzetten van koolwater- stoffen.
CA1124195A (en) * 1980-03-26 1982-05-25 Chandra P. Khulbe 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
WO1985004670A3 (en) 1985-11-21
EP0159867A3 (en) 1986-01-15
ES8606465A1 (es) 1986-04-01
EP0159867A2 (de) 1985-10-30
WO1985004670A2 (en) 1985-10-24
JPS61501855A (ja) 1986-08-28
ES542204A0 (es) 1986-04-01

Similar Documents

Publication Publication Date Title
CA1080202A (en) Hydroconversion of coal in a hydrogen donor solvent
US5374348A (en) Hydrocracking of heavy hydrocarbon oils with heavy hydrocarbon recycle
US4695369A (en) Catalytic hydroconversion of heavy oil using two metal catalyst
US4294686A (en) Process for upgrading heavy hydrocarbonaceous oils
US3622498A (en) Slurry processing for black oil conversion
CA1218321A (en) Integrated process for the solvent refining of coal
GB1574371A (en) Process for the production of hydrocarbons from carbonaceous solids containing volatilisable hydrocarbons
GB1590963A (en) Manufacture of hydrocarbon oil by hydrocracking of coal
EP0177307B1 (de) Katalytische Hydrokonvertierung von Kohlenstoff enthaltenden Materialien
US4486293A (en) Catalytic coal hydroliquefaction process
NL8204253A (nl) Werkwijze voor het katalytisch hydrogenerend omzetten van een asfaltenenbevattende petroleumtoevoer.
GB1589423A (en) Hydrogen conversion process
GB2093058A (en) Simultaneous demetalization and hydrocracking of heavy
US3862899A (en) Process for the production of synthesis gas and clean fuels
US4201659A (en) Process for the preparation of gas oil
WO1980001283A1 (en) Integrated coal liquefaction-gasification process
JPS5874785A (ja) 重質炭化水素油の水素化分解法
US4551224A (en) Coal liquefaction process
US3844937A (en) Hydroconversion of tar sand bitumens
US4120778A (en) Process for the conversion of hydrocarbons in atmospheric crude residue
US4534847A (en) Process for producing low-sulfur boiler fuel by hydrotreatment of solvent deashed SRC
US4405442A (en) Process for converting heavy oils or petroleum residues to gaseous and distillable hydrocarbons
SU812186A3 (ru) Способ получени углеводородовиз угл
EP0035864B1 (de) Verfahren zum Verbessern schwerer Kohlenwasserstofföle
EP0159867B1 (de) Verfahren zur Wasserstoffumwandlung von schweren, Sulfur enthaltenden Kohlenwasserstoffen mit Synthesegas

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE FR GB IT NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE FR GB IT NL SE

17P Request for examination filed

Effective date: 19860609

17Q First examination report despatched

Effective date: 19870410

ITF It: translation for a ep patent filed

Owner name: LENZI & C.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE FR GB IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19880131

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890216

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19890331

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890412

Year of fee payment: 5

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890430

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19900430

BERE Be: lapsed

Owner name: THE BRITISH PETROLEUM CY P.L.C.

Effective date: 19900430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19901101

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19901228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST