WO2002088021A1 - Procede d'oxydation d'une charge hydrocarbonee - Google Patents

Procede d'oxydation d'une charge hydrocarbonee Download PDF

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Publication number
WO2002088021A1
WO2002088021A1 PCT/EP2001/004852 EP0104852W WO02088021A1 WO 2002088021 A1 WO2002088021 A1 WO 2002088021A1 EP 0104852 W EP0104852 W EP 0104852W WO 02088021 A1 WO02088021 A1 WO 02088021A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
feedstock
mole
containing gas
hydrocarbonaceous feedstock
Prior art date
Application number
PCT/EP2001/004852
Other languages
English (en)
Inventor
Grahame Yarvic Buss
Herman Pieter Charles Eduard Kuipers
Hendrik Martinus Wentinck
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to PCT/EP2001/004852 priority Critical patent/WO2002088021A1/fr
Publication of WO2002088021A1 publication Critical patent/WO2002088021A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components

Definitions

  • the present invention relates to a process for the oxidation of a hydrocarbonaceous feedstock, in particular a process for the catalytic partial oxidation of a hydrocarbonaceous feedstock.
  • Partial oxidation of a hydrocarbonaceous feedstock, in particular hydrocarbons, in the presence of a catalyst is an attractive route for the preparation of mixtures of carbon monoxide and hydrogen, normally referred to as synthesis gas.
  • the partial oxidation of hydrocarbons is an exothermic reaction represented by the equation: c n H 2n+2 + n / 2 O2 " n CO + (n+1) H2
  • the catalytic partial oxidation reaction proceeds at very short contact times (in the order of tens of milliseconds), it is important that the reactants are well-mixed when brought into contact with the catalyst. Otherwise, the reaction will proceed at an undesirable stoichiometry and the desired product selectivity will not be obtained.
  • the mixture of the reactants of the catalytic partial oxidation process i.e. a hydrocarbonaceous feedstock and an oxygen-containing gas, is highly reactive and explosive, especially at the mixing conditions which are typically applied, i.e. at elevated temperature and pressure -and in amounts giving an oxygen-to-carbon ratio in the range of from 0.3 to 0.8.
  • This finding may be advantageously applied in the above-mentioned catalytic partial oxidation process. It will be appreciated that the present finding may also be applied in other oxidation processes wherein a mixture of hydrocarbonaceous feedstock and oxygen-containing gas may be formed prior to the actual oxidation.
  • Non-limiting examples of such oxidation processes are non-catalytic partial oxidation, combustion, e.g. in a gas turbine, and the oxidation step in autothermal reforming.
  • the present invention relates to a process for the oxidation of a hydrocarbonaceous feedstock with an oxygen-containing gas, wherein the hydrocarbonaceous feedstock is mixed with the oxygen- containing gas prior to oxidation in an oxidation zone and wherein an oxidant is added to the hydrocarbonaceous feedstock before the feedstock is mixed with the oxygen- containing gas in an amount in the range of from 0.005 to 10% (mole/mole) of oxidant based on the feedstock.
  • oxidant is especially advantageous in oxidation processes wherein the hydrocarbonaceous feedstock and the oxygen-containing gas are mixed at elevated temperature and/or at elevated pressure.
  • elevated temperature and pressure is to temperatures well above room temperature and pressures well above atmospheric pressure.
  • the mixture of hydrocarbonaceous feedstock and oxygen-containing gas preferably has a temperature in the range of from 100 to 800 °C, more preferably of from 150 to 600 °C, even more preferably of from 200 to 400 °C.
  • the pressure at which the feedstock and the oxygen-containing gas are mixed is preferably in the range of from 2 to 100 bar (absolute) , more preferably of from 5 to 80 bar (absolute) , even more preferably of from 10 to 50 bar (absolute) .
  • the oxidant to be added is preferably oxygen or water, more preferably oxygen.
  • Oxygen may be added as substantially pure oxygen or as a diluted oxygen stream, such as air or oxygen-enriched air. If the oxidant is water, it is preferred to add the water as steam. Alternatively, atomised liquid water may be added to a preheated stream of the hydrocarbonaceous feedstock.
  • the oxidant is added to the hydrocarbonaceous feedstock before the feedstock is mixed with the oxygen-containing gas, i.e. upstream of the zone where the feedstock and the oxygen-containing gas are mixed.
  • the oxidant may for example be injected into the conduit supplying the feedstock to the mixing zone. It is advantageous to add the oxidant well before the mixing zone such that the oxidant is well-mixed through the hydrocarbonaceous feedstock when the feedstock is mixed with the oxygen-containing gas.
  • the residence time of the oxidant in the stream of hydrocarbonaceous feedstock before it is entering the mixing zone is at least 0.5 second, more preferably at least 1 second.
  • the feedstock and the oxygen-containing gas are preheated before mixing them.
  • the oxidant may be added to the feedstock before the feedstock is preheated or to the preheated feedstock.
  • the amount of oxidant added to the feedstock must be below the flammability limit of the thus-obtained feedstock-oxidant mixture, i.e. the amount may not be so high that ignition or explosion of the feedstock-oxidant mixture occurs at the prevailing process conditions.
  • the oxidant is added in an amount in the range of from 0.01 to 5% (mole/mole) based on the feedstock, more preferably of from 0.02 to 2% (mole/mole), even more preferably of from 0.05 to 1% (mole/mole), in particular of from 0.05 to 0.5% (mole/mole) .
  • Suitable hydrocarbonaceous feedstocks comprise hydrocarbons, oxygenates or mixtures thereof.
  • Oxygenates are defined as molecules containing apart from carbon and hydrogen atoms at least 1 oxygen atom which is linked to either one or two carbon atoms or to a carbon atom and a hydrogen atom.
  • suitable oxygenates are methanol, ethanol, dimethyl ether and the like.
  • Preferred hydrocarbonaceous feedstocks comprise methane, natural gas, associated gas or other sources of "light hydrocarbons".
  • the term "light hydrocarbon” is a reference to hydrocarbons having 1 to 5 carbon -atoms .
  • the feedstock comprises methane in an amount of at least 50% by volume, more preferably at least 70% by volume, even more preferably at least 80% by volume.
  • the oxygen-containing gas that is mixed with the hydrocarbonaceous feedstock prior to oxidation may be oxygen, air, or oxygen-enriched air, preferably oxygen.
  • the oxidation process of the present invention is preferably a combustion process or a partial oxidation process, more preferably a catalytic partial oxidation process .
  • a mixture of hydrocarbonaceous feedstock and oxygen-containing gas is contacted with a catalyst to obtain synthesis gas by means of an exothermic reaction.
  • Suitable catalysts are known in the art.
  • the hydrocarbonaceous feedstock and the oxygen-containing gas are preferably present in the mixture in such amounts as to give an oxygen-to-carbon ratio in the range of from 0.3 to 0.8, more preferably, in the range of from 0.45 to 0.75.
  • References herein to the oxygen-to-carbon ratio refer to the ratio of oxygen in the form of molecules (O2) to carbon atoms present in the hydrocarbon feedstock. Oxygen-to-carbon ratios in the region of the stoichiometric ratio of 0.5, i.e. ratios in the range of from 0.45 to 0.65, are especially preferred. If oxygenate feedstocks are used, e.g. methanol, oxygen-to-carbon ratios below 0.3 can suitably be used.
  • the mixture of hydrocarbonaceous feedstock and oxygen-containing gas may optionally comprise steam. If steam is present, the steam-to-carbon ratio is preferably in the range of from above 0.0 to 3.0, more preferably from 0.0 -to 2.0. Optionally, the mixture may comprise carbon dioxide.
  • the hydrocarbonaceous feedstock and the oxygen- containing gas are preferably preheated, resulting in a preheated mixture of hydrocarbonaceous feedstock and oxygen-containing gas. It is an advantage of the catalytic partial oxidation process according to the present invention that the mixture may be heated to a relatively high temperature without the occurrence of ignition or explosion upstream of the catalyst.
  • the temperature of the mixture is in the range of from 100 to 800 °C. Due to the exothermic character of the catalytic partial oxidation reaction, the temperature of the gas leaving the catalyst is typically in the range of from 750 to 1400 °C, preferably of from 850 to 1350 °C.
  • the mixture may be contacted with the catalyst at any suitable gas hourly space velocity (expressed as normal litres of gas per kilogram of catalyst at STP conditions) .
  • gas hourly space velocity is in the range of from 20,000 to 100,000,000 Nl/kg/h, more preferably of from 50,000 to 50,000,000 Nl/kg/h, even more preferably of from 100,000 to 30,000,000 Nl/kg/h.
  • Example 2 The same experiment as in Example 1 was carried out, without addition of oxygen to the natural gas stream. Ignition was observed at a temperature of the mixture in the mixing zone of 278 °C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un procédé permettant d'oxyder une charge hydrocarbonée à l'aide d'un gaz contenant de l'oxygène, la charge hydrocarbonée étant mélangée avec un gaz contenant de l'oxygène avant l'oxydation dans une zone d'oxydation, et un oxydant étant ajouté à la charge hydrocarbonée avant que cette dernière soit mélangée au gaz contenant de l'oxygène dans une quantité comprise entre 0,005% et 10% (mole/mole) de l'oxydant par rapport à la charge.
PCT/EP2001/004852 2001-04-27 2001-04-27 Procede d'oxydation d'une charge hydrocarbonee WO2002088021A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/004852 WO2002088021A1 (fr) 2001-04-27 2001-04-27 Procede d'oxydation d'une charge hydrocarbonee

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/004852 WO2002088021A1 (fr) 2001-04-27 2001-04-27 Procede d'oxydation d'une charge hydrocarbonee

Publications (1)

Publication Number Publication Date
WO2002088021A1 true WO2002088021A1 (fr) 2002-11-07

Family

ID=8164396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/004852 WO2002088021A1 (fr) 2001-04-27 2001-04-27 Procede d'oxydation d'une charge hydrocarbonee

Country Status (1)

Country Link
WO (1) WO2002088021A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138438A (en) * 1960-06-01 1964-06-23 Renault Methods for converting methane
JPS498633B1 (fr) * 1968-08-29 1974-02-27
US4089639A (en) * 1974-11-26 1978-05-16 John Zink Company Fuel-water vapor premix for low NOx burning
EP0629578A1 (fr) * 1993-06-18 1994-12-21 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle catalytique d'hydrocarbone
EP0673877A1 (fr) * 1994-03-25 1995-09-27 Exxon Research And Engineering Company Préparation de gaz de synthèse
EP0842894A1 (fr) * 1996-11-15 1998-05-20 Haldor Topsoe A/S Méthode et dispositif pour l'oxydation partielle catalytique d'un hydrocarbure
WO2001018451A1 (fr) * 1999-09-06 2001-03-15 Shell Internationale Research Maatschappij B.V. Dispositif melangeur
EP1095903A1 (fr) * 1999-10-28 2001-05-02 Shell Internationale Researchmaatschappij B.V. Procédé pour l'oxydation d'une charge d'hydrocarbures

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138438A (en) * 1960-06-01 1964-06-23 Renault Methods for converting methane
JPS498633B1 (fr) * 1968-08-29 1974-02-27
US4089639A (en) * 1974-11-26 1978-05-16 John Zink Company Fuel-water vapor premix for low NOx burning
EP0629578A1 (fr) * 1993-06-18 1994-12-21 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle catalytique d'hydrocarbone
EP0673877A1 (fr) * 1994-03-25 1995-09-27 Exxon Research And Engineering Company Préparation de gaz de synthèse
EP0842894A1 (fr) * 1996-11-15 1998-05-20 Haldor Topsoe A/S Méthode et dispositif pour l'oxydation partielle catalytique d'un hydrocarbure
WO2001018451A1 (fr) * 1999-09-06 2001-03-15 Shell Internationale Research Maatschappij B.V. Dispositif melangeur
EP1095903A1 (fr) * 1999-10-28 2001-05-02 Shell Internationale Researchmaatschappij B.V. Procédé pour l'oxydation d'une charge d'hydrocarbures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 197412, Derwent World Patents Index; Class E36, AN 1974-22205V, XP002133587 *

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