EP0318903B1 - Verfahren zur Hydrierung flüssiger kohlenstoffhaltiger Einsatzstoffe - Google Patents

Verfahren zur Hydrierung flüssiger kohlenstoffhaltiger Einsatzstoffe Download PDF

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Publication number
EP0318903B1
EP0318903B1 EP88119848A EP88119848A EP0318903B1 EP 0318903 B1 EP0318903 B1 EP 0318903B1 EP 88119848 A EP88119848 A EP 88119848A EP 88119848 A EP88119848 A EP 88119848A EP 0318903 B1 EP0318903 B1 EP 0318903B1
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EP
European Patent Office
Prior art keywords
flow
hydrogenation
gas
batch
hydrogenation gas
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
EP88119848A
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German (de)
English (en)
French (fr)
Other versions
EP0318903A2 (de
EP0318903A3 (en
Inventor
Wolfdieter Klein
Claus Strecker
Alfons Feuchthofen
Ulrich Bönisch
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.)
Veba Oel Technologie und Automatisierung GmbH
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Veba Oel Technologie und Automatisierung GmbH
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Publication of EP0318903A2 publication Critical patent/EP0318903A2/de
Publication of EP0318903A3 publication Critical patent/EP0318903A3/de
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Publication of EP0318903B1 publication Critical patent/EP0318903B1/de
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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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions

Definitions

  • the invention relates to a process for the hydrogenation of liquid carbonaceous feedstocks such as heavy oils, oil residues, top or vacuum residues, syncrude from oil shale, tar sands, tars and pitches from hard coal or lignite, with hydrogen-containing gases as hydrogenation gas under the conditions of a phase-phase hydrogenation at elevated temperature and increased pressure in the presence of an additive or a catalyst with a downstream hot separator stage with separate heating of a feed stream formed from the feed materials and a partial stream of the hydrogenation gas and a second partial stream of the hydrogenation gas.
  • the feedstocks are liquid either at normal temperature or at elevated temperatures.
  • Temperatures in the bottom phase reactor of approximately 400 to 500 ° C. are typical, and the process pressure can be selected between 150 to 1200 bar.
  • the invention is based on a method as specified above, in which heavy oil is fed as a feed product to a preheater and in which a partial flow of the total amount of hydrogenation gas required in a gas heat exchanger through which the hot separator head product flows precedes the preheated mixture of heavy oil, possibly additive and hydrogenation gas Entry into the bottom phase reactor is added (see. DE 35 23 709 A1).
  • the publication DE 35 05 553 A1 relates to a process for pretreating the feed products for the coal hydrogenation and is otherwise analogous to the above Process according to DE 35 23 709 A1.
  • the feed products are heated to the temperature required for entry into the reaction system of the bottom phase hydrogenation by means of a heating furnace provided in the feed product stream.
  • This heating furnace is one of the most critical components of any sump phase hydrogenation system. This is due in particular to the operating conditions, which are characterized by high hydrogen partial pressure in the pipe, high pipe wall temperatures and high total pressure, and which set operational limits beyond the material that can be used.
  • tip preheaters are associated with procedural disadvantages which result from high pressure loss in the preheater, poor heat transfer and undefined conditions due to the three-phase system present in the tube.
  • the task of the invention is to improve the overall heat management of the process by recovering the heat of reaction.
  • DE 26 51 253 A1 it is stated that in a procedure similar to that at the beginning The specified process of the preheater heated by external heat can be considerably reduced or even completely omitted under certain circumstances, but it is intended that a distillate fraction to be returned to the feed product is reheated in a heat exchanger heated by external heat.
  • the additional heating of the distillates brings the advantage of the significantly lower tendency to coke compared to the heating of the coal pulp in a preheater.
  • the above object is achieved in the method of the type mentioned above in that the hot separator head product emits its heat to the feed streams mentioned in indirect heat exchange and that by further heating the separately conducted part of the hydrogenation gas in a hydrogenation gas heater and then combining it with the indirect heat exchange heated feed stream the necessary inlet temperature is reached in the bottom phase reactor.
  • the specified method is suitable for hydrating liquid carbon-containing feedstocks such as heavy oils, oil residues (top and vacuum residues), syncrude from e.g. B. oil shale, tar sands, heavy oils, tars and pitches from hard coal or lignite u. to process.
  • liquid carbon-containing feedstocks such as heavy oils, oil residues (top and vacuum residues), syncrude from e.g. B. oil shale, tar sands, heavy oils, tars and pitches from hard coal or lignite u. to process.
  • the present process is also advantageous Oils or heavy mineral oil residues
  • Mixtures of finely ground coal and the feedstocks provided according to the invention are supplied as so-called foreign oils ("co-processing").
  • Such a procedure has the advantage that the recycle streams required for the mashing of the finely ground coal are largely or completely eliminated.
  • Weight ratios of coal and foreign oil of 1 to 5 to 4 to 5 are preferred. All types of coal which can be economically hydrogenated, for example, are suitable as the coal to be used.
  • the process can be designed by recovering the thermal energy of the reaction products as far as possible so that a hydrogenation gas heater is sufficient for a separate partial flow of the hydrogenation gas in order to apply the start-up temperature of the hydrogenation reaction required when starting up into the hydrogenation reactor in the bottom phase and to compensate for heat losses .
  • This result could only be achieved by optimizing the process control of the reaction products and the feed products in countercurrent, and it is surprising that the thermal energy to be supplied can be introduced into the process via a partial stream of the hydrogenation gas without external heating of the liquid or solid-liquid feed products.
  • Circulation furnaces come as hydrogenation gas heaters, hereinafter also referred to as hydrogenation gas furnaces, but preferably also radiation ovens, in which heating to a temperature of 300 to 650 ° C., preferably 490 to 550 ° C. takes place.
  • stream (9) in the downstream direction comes into heat exchange relationship with the feed stream (3) in the heat exchanger (20) and the partial stream of the hydrogenation gas (5) in the heat exchanger (23) and passes through a reactor (27) for hydrogenation in the gas phase at a fixed bed contact .
  • the product stream refined in reactor (27) passes as stream (10) heat exchanger (19) and heat exchanger (22) in heat exchange relationship with stream (3) or stream (5) and an intermediate separator (28) with separation of a hot oil fraction (11).
  • the residual stream (12) drawn off by the separator (28) gives the rest of the heat exchangers (18) and (21) for heating the Use products utilizable heat to electricity (3) and electricity (5) and is fed to a cold separator (29), in which a separation of waste water and exhaust gas as well as the recovery of a cold oil fraction (13) and recycling of the cycle hydrogenation gas as stream (15) via compressor (30) done in the process.
  • part of the circulating gas stream (16) is advantageously kept available as a quench gas stream and fed in if necessary.
  • a gas scrubber can be provided in the usual way for working up the circulating hydrogen gas fraction. Such a work-up ensures a sufficient hydrogen partial pressure in the hydrogenation gas system by removing the C1 to C4 components which are soluble in the gas scrubbing by means of washing liquid.
  • the separate partial stream from the total amount of hydrogenation gas to be used can make up 20 to 95, preferably 40 to 80% of the total amount of hydrogenation gas required.
  • the stream of feedstocks (1) consisting of a suspension with the additive or catalyst is mixed with a partial stream of the hydrogenation gas (2) composed of cycle hydrogenation gas, stream (15), via compressor (30) while feeding in fresh hydrogen, stream (17). combined to form stream (3) and preheated to the conditions of stream (4) by means of indirect heat exchange in the apparatuses (18), (19) and (20).
  • the separate hydrogenation gas stream (5) is also preheated in indirect heat exchange in the apparatuses (21), (22) and (23) and heated to the necessary temperature in hydrogenation gas heater (24), so that in the mixture of material stream (6) with the Material flow (4) the required reactor inlet temperature in reactor (25) for stream (7) is reached.
  • the desired products are obtained in the reactor (25) or in a cascade of reactors connected in series, which are separated in the hot separator (26) into a residue stream (8) and into a top stream (9).
  • the top stream (9) is used for preheating in countercurrent to the feed stream (3) and hydrogenation gas stream (5) in the aforementioned apparatuses (18), (19), (20), (21), (22) and (23).
  • the circuit shown in the figure provides an integrated gas phase reactor (27) for the purpose of refining and further removal, in particular of the O, S and N-containing heteroatom components.
  • Gas phase reactor (27) is advantageously connected between apparatus (23) and apparatus (19).
  • the products condensed in the heat exchangers due to the removal of heat are collected in intermediate separators (28) and in cold separators (29).
  • the condensates are discharged from the high-pressure circuit as hot oil (11) and cold oil (13). After the hot oil has been drawn off, water can be injected in order to avoid the salinization of the downstream heat exchangers.
  • the water of reaction formed in the hydrogenation process is optionally separated together with the injection water in the cold separator (29) and discharged as stream (14) from the high-pressure circuit. It contains u. a. the heteroatom compounds removed by refining in the form of the simple hydrogen compounds H2S and in particular NH3 dissolved in the waste water.
  • the temperature in the intermediate separator can be freely selected within a certain range.
  • the residual gas going overhead in the cold separator (29) is returned with a circuit compressor (30), if necessary after a certain proportion has been discharged.
  • the return gas is cold gas as a stream for temperature control of the reactors and the hot separator (16) taken.
  • the fresh hydrogen required for the reaction is added as stream (17). Provision can also be made to add stream (2) as a fresh hydrogen stream.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP88119848A 1987-12-04 1988-11-29 Verfahren zur Hydrierung flüssiger kohlenstoffhaltiger Einsatzstoffe Expired - Lifetime EP0318903B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3741105 1987-12-04
DE19873741105 DE3741105A1 (de) 1987-12-04 1987-12-04 Verfahren zur hydrierung fluessiger kohlenstoffhaltiger einsatzstoffe

Publications (3)

Publication Number Publication Date
EP0318903A2 EP0318903A2 (de) 1989-06-07
EP0318903A3 EP0318903A3 (en) 1990-05-02
EP0318903B1 true EP0318903B1 (de) 1992-11-25

Family

ID=6341871

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88119848A Expired - Lifetime EP0318903B1 (de) 1987-12-04 1988-11-29 Verfahren zur Hydrierung flüssiger kohlenstoffhaltiger Einsatzstoffe

Country Status (8)

Country Link
US (1) US4983279A (enrdf_load_stackoverflow)
EP (1) EP0318903B1 (enrdf_load_stackoverflow)
JP (1) JPH01207386A (enrdf_load_stackoverflow)
AU (1) AU620056B2 (enrdf_load_stackoverflow)
CA (1) CA1316862C (enrdf_load_stackoverflow)
DE (2) DE3741105A1 (enrdf_load_stackoverflow)
PL (1) PL158169B1 (enrdf_load_stackoverflow)
ZA (1) ZA889071B (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5738779A (en) * 1996-07-18 1998-04-14 Texaco Inc. Hydrotreating process with two phase flow splitting and heat recovery
US8944069B2 (en) * 2006-09-12 2015-02-03 Vidacare Corporation Assemblies for coupling intraosseous (IO) devices to powered drivers
EP2792729A1 (en) 2013-04-17 2014-10-22 XTLgroup bv Process for hydroprocessing a liquid feed comprising hydrocarbons into fuel components

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU522767B2 (en) * 1979-08-24 1982-06-24 Gulf Research & Development Company Coal hydrogenation
AU522787B2 (en) * 1979-08-24 1982-06-24 Gulf Research & Development Company Coal liquefaction
DE2936008A1 (de) * 1979-09-06 1981-04-02 Saarbergwerke AG, 6600 Saarbrücken Verfahren zum hydrieren von kohle
DE3105030A1 (de) * 1981-02-12 1982-09-02 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von kohlenwasserstoffoelen aus kohle durch druckhydrierung in zwei stufen
CA1238287A (en) * 1984-08-04 1988-06-21 Werner Dohler Process for the production of reformer feed and heating oil or diesel oil from coal
EP0177676B1 (de) * 1984-09-13 1992-03-04 Ruhrkohle Aktiengesellschaft Verfahren zur Prozesseinstellung mit Wärmerückgewinnung für die Sumpfphasehydrierung mit integrierter Gasphasehydrierung
DE3505553C2 (de) * 1985-02-18 1987-04-30 Veba Oel Entwicklungs-Gesellschaft mbH, 4650 Gelsenkirchen Verfahren zur Vorbehandlung der Einsatzprodukte für die Kohlehydrierung
DE3523709A1 (de) * 1985-07-03 1987-01-08 Veba Oel Entwicklungs Gmbh Verfahren zur vorbehandlung der einsatzprodukte fuer die schweroelhydrierung

Also Published As

Publication number Publication date
DE3741105C2 (enrdf_load_stackoverflow) 1990-01-04
PL158169B1 (en) 1992-08-31
DE3741105A1 (de) 1989-06-15
AU2645888A (en) 1989-06-08
ZA889071B (en) 1989-08-30
US4983279A (en) 1991-01-08
DE3876219D1 (de) 1993-01-07
AU620056B2 (en) 1992-02-13
CA1316862C (en) 1993-04-27
EP0318903A2 (de) 1989-06-07
JPH01207386A (ja) 1989-08-21
EP0318903A3 (en) 1990-05-02
PL276160A1 (en) 1989-07-24

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