WO2000001613A1 - Process for autothermal reforming of a hydrocarbon feedstock - Google Patents

Process for autothermal reforming of a hydrocarbon feedstock Download PDF

Info

Publication number
WO2000001613A1
WO2000001613A1 PCT/EP1999/004561 EP9904561W WO0001613A1 WO 2000001613 A1 WO2000001613 A1 WO 2000001613A1 EP 9904561 W EP9904561 W EP 9904561W WO 0001613 A1 WO0001613 A1 WO 0001613A1
Authority
WO
WIPO (PCT)
Prior art keywords
steam
hydrocarbon feedstock
oxygen containing
stream
process according
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.)
Ceased
Application number
PCT/EP1999/004561
Other languages
French (fr)
Inventor
Peter Seier Christensen
Thomas Sandahl Christensen
Ivar Ivarsen Primdahl
Jens-Henrik Bak Hansen
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.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8098778&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000001613(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Priority to AT99932778T priority Critical patent/ATE307778T1/en
Priority to DE69927976T priority patent/DE69927976T2/en
Priority to JP2000558025A priority patent/JP4154123B2/en
Priority to EP99932778A priority patent/EP1098838B1/en
Priority to US09/720,652 priority patent/US6689294B1/en
Priority to AU49044/99A priority patent/AU754632B2/en
Publication of WO2000001613A1 publication Critical patent/WO2000001613A1/en
Priority to NO20006713A priority patent/NO20006713L/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using oxygen; using 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/06—Integration with other chemical processes
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/169—Controlling the feed
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the preser. invention is directed to soot free autothermal reforming (ATR) of hydrocarbon feed.
  • soot formation may be avoided by using a specific burner design and through controlling the operating conditions of the ATR process. Soot is formed in the flame of an autothermal reactor within certain ranges of operating conditions. When the amount cf steam relative to the other components passed to the ATR reaction is under a certain critical value, soot is formed ir. the reacting feed.
  • the limiting amount of steam can be expressed as the critical steam to carbon ratio, calculated as the molar flow rate of steam to the molar flow race of carbon in the hydrocarbon feed.
  • the hydrocarbon feedstock can be in form of natural gas or another kind of hydrocarbon including LPG, butane, naphtha, etc.
  • the molar flow rate of carbon is calculated as the molar flow rate of the hydrocarbon times the carbon content of the hydrocarbon.
  • the design of the burner nozzles has influence on the critical steam to carbon ratio. One such burner useful r. ATR is described in US Patent No. 5,496,170.
  • the process is operated at low steam to carbon radios, since a low ratio lowers the investment expenses for an ATR plant and reduces the necessary energy consumption in operating the plant. Additionally, a low steam to carbon ratio makes it possible to optimise the produced synthesis gas composition for production of CO-rich gases for e.g. methanol or dimethyl ether synthesis and Fisher-Tropsh processes.
  • the feed to the ATR is divided into two separate streams, which are send to the burner.
  • One stream contains oxygen and steam.
  • the other stream contains hydrocarbon and steam and optionally hydrogen and/or carbondioxide .
  • the two streams are mixed downstream the burner and combustion takes place.
  • the critical steam to carbon ratio depends on the distribution of steam to the oxygen and hydrocarbon feed stream. When the amount of steam contained in the oxygen feed stream is reduced the critical steam to carbon ratio is reduced.
  • this invention provides a process for the preparation of a hydrogen and/or carbonmonoxide rich gas comprising the step of partial oxidation of a hydrocarbon feedstock with an oxygen containing reactant stream in presence of steam, wherein the steam is present ir. the hydrocarbon feedstock in an amount higher than in the oxygen containing reactant stream.
  • the invention allows operation of the process at a lower steam to carbon ratio compared to the critical steam/carbon ratio at equal distribution of steam between the oxygen and the hydrocarbon containing streams .
  • the distance to the critical steam to carbon ratio is thereby by the invention reduced and the risk of soot formation in case of a change in operating conditions e.g. in case of an upset in the feed supply.
  • the test unit employed consists of a system for providing the feeds to the ATR reactor, the ATR reactor itself, and equipment for post treatment of the product gas .
  • the feed streams consist of natural gas, steam, oxygen, and hydrogen. All gases are compressed to operating pressure and preheated to operating temperature. Natural gas is desulphurized before entering the ATR reactor. The feeds were combined into two streams and were send to the burner of the ATR. A first feed stream of natural gas, hydrogen, and steam was heated to 500°C. A second feed stream containing oxygen and steam was heated to 220°C.
  • the substoichiometric combustion and a subsequent catalytic steam reforming and shift reactions were carried out.
  • the inlet and exit gas compositions are analyzed by gaschromatography.
  • the product gas was in equilibrium with respect to the reforming and shift reactions.
  • the hydrocarbon used was natural gas.
  • the composition of the natural gas is summarized in Table 2.
  • the flow rates were in all below described tests 102 Nm 3 /hr natural gas and 3 Nm 3 /h hydrogen.
  • 100 Nm 3 /h natural gas correspond to a carbon flow rate of 103 Nm 3 /h.
  • the oxygen flow rate was adjusted to obtain the desired operating temperature and varied in the range 58-61 Nm 3 /h.
  • the adiabatic ATR exit temperature will be higher than the temperature given in Table 3. This means that if a large unit, frcrr. which the heat loss is negligible, is subjected to exact the same conditions, the ATR exit temperature will be close to the adiabatic ATR exit temperature.
  • the composition of the product gas from the ATR reactor in the tests of Table 3 was measured by gaschromatography. Selected gas compositions are shown in Table 4. The gas composition is given as dry mole%, which is the mole composition of the gas components when steam is not included.
  • the data in Table 3 clearly demonstrate the influence of the steam distribution on the critical steam to carbon ratio.
  • the critical steam to carbon ratio is 44% higher in test number 1.1 than in test number 1.3.
  • the steam concentration in the oxygen containing feed stream is 29% in test 1.1 and 5% in test 1.3.
  • a similar but less pronounced influence is seen at higher temperature.
  • the critical steam to carbon ratio is 15% higher in test number 2.1 than in test number 2.2, where the steam concentrations are 24% and 6% respectively in the oxygen containing stream.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

Process for the preparation of a hydrogen and/or carbonmonoxide rich gas comprising the step of partial oxidation of a hydrocarbon feedstock with an oxygen containing reactant stream in presence of steam, wherein the steam is present in the hydrocarbon feedstock in an amount higher than in the oxygen containing reactant stream.

Description

-ϊ-
Process for Autothermal Reforming of a Hydrocarbon
Feedstock
The preser. invention is directed to soot free autothermal reforming (ATR) of hydrocarbon feed.
In autothermal reforming, combustion of hydrocarbon feed is carried cut with substoichiometric amounts of oxygen by flame reactions in a burner combustion zone and, subsequently, steam reforming of the partially combusted feedstock in a fixed bed of steam reforming catalyst. Substoichiometric combustion of hydrocarbons leads disad- vantageously to formation of soot. Soot formation may be avoided by using a specific burner design and through controlling the operating conditions of the ATR process. Soot is formed in the flame of an autothermal reactor within certain ranges of operating conditions. When the amount cf steam relative to the other components passed to the ATR reaction is under a certain critical value, soot is formed ir. the reacting feed. The limiting amount of steam can be expressed as the critical steam to carbon ratio, calculated as the molar flow rate of steam to the molar flow race of carbon in the hydrocarbon feed. The hydrocarbon feedstock can be in form of natural gas or another kind of hydrocarbon including LPG, butane, naphtha, etc. The molar flow rate of carbon is calculated as the molar flow rate of the hydrocarbon times the carbon content of the hydrocarbon. The design of the burner nozzles has influence on the critical steam to carbon ratio. One such burner useful r. ATR is described in US Patent No. 5,496,170.
Examples cf operating conditions, which do not result in soot forr.arion, are summarized in a paper by Christensen and Pritr.dahl (Hydrocarbon processing, March 1994, pages 39-46) . The conditions disclosed in this paper are shown i Table 1. Due to heat loss from the relatively small pilot unit employed in the experiments of Christensen and Prim- dahl to :r.e adiabatic ATR exit temperature will be higher than the temperature given in Table 1. This means that if a large unit, from which the heat loss is negligible, is subjected to the exact same conditions, the ATR exit temperature will be close to the adiabatic ATR exit temperature .
Advantageously, the process is operated at low steam to carbon radios, since a low ratio lowers the investment expenses for an ATR plant and reduces the necessary energy consumption in operating the plant. Additionally, a low steam to carbon ratio makes it possible to optimise the produced synthesis gas composition for production of CO-rich gases for e.g. methanol or dimethyl ether synthesis and Fisher-Tropsh processes.
The feed to the ATR is divided into two separate streams, which are send to the burner. One stream contains oxygen and steam. The other stream contains hydrocarbon and steam and optionally hydrogen and/or carbondioxide . The two streams are mixed downstream the burner and combustion takes place.
It has now been found that the critical steam to carbon ratio depends on the distribution of steam to the oxygen and hydrocarbon feed stream. When the amount of steam contained in the oxygen feed stream is reduced the critical steam to carbon ratio is reduced.
Description of the Invention
Based on zhe above findings, this invention provides a process for the preparation of a hydrogen and/or carbonmonoxide rich gas comprising the step of partial oxidation of a hydrocarbon feedstock with an oxygen containing reactant stream in presence of steam, wherein the steam is present ir. the hydrocarbon feedstock in an amount higher than in the oxygen containing reactant stream. The invention allows operation of the process at a lower steam to carbon ratio compared to the critical steam/carbon ratio at equal distribution of steam between the oxygen and the hydrocarbon containing streams . The distance to the critical steam to carbon ratio is thereby by the invention reduced and the risk of soot formation in case of a change in operating conditions e.g. in case of an upset in the feed supply.
Below is the inventive process illustrated at a steam content in the oxygen containing stream down to an amount of 5%, but the process will be applicable also at lower steam concentrations .
Example
The test unit employed consists of a system for providing the feeds to the ATR reactor, the ATR reactor itself, and equipment for post treatment of the product gas .
The feed streams consist of natural gas, steam, oxygen, and hydrogen. All gases are compressed to operating pressure and preheated to operating temperature. Natural gas is desulphurized before entering the ATR reactor. The feeds were combined into two streams and were send to the burner of the ATR. A first feed stream of natural gas, hydrogen, and steam was heated to 500°C. A second feed stream containing oxygen and steam was heated to 220°C.
In the ATR reactor, the substoichiometric combustion and a subsequent catalytic steam reforming and shift reactions were carried out. The inlet and exit gas compositions are analyzed by gaschromatography. The product gas was in equilibrium with respect to the reforming and shift reactions.
Downstrearr. the ATR reactor, the process gas was cooled dowr. and the majority of the steam content of the product gas condensed. Any soot formed during the above reaction will be captured in the condensate. The condensate was subjected to both gravimetric and spectrophotometric analyse .
The following tests were carried out to illustrate the influence of steam distribution on the critical steam to carbon ratios according to the invention. The hydrocarbon used was natural gas. The composition of the natural gas is summarized in Table 2.
Table 2
Figure imgf000006_0001
Each test was made by approaching the critical steam to carbon ratio from the steam rich side. The tests were initiated with a sufficiently high steam flow to ensure soot free conditions. The steam flow was then decreased stepwise to a steam to carbon ratio of approximately 0.03. The syster. was allowed to become stable after which the condensate was examined for soot content. If the condensate was still soot free, the next step was taken. The term "soot free conditions" refers to condition in which the soot formation is negligible. The soot amount formed at the critical steam to carbon ratio was approximately 3-5 ppm. Table 3 shows the critical steam to carbon ratio at two different temperature levels and at varying steam distribution. The flow rates were in all below described tests 102 Nm3/hr natural gas and 3 Nm3/h hydrogen. 100 Nm3/h natural gas correspond to a carbon flow rate of 103 Nm3/h. The oxygen flow rate was adjusted to obtain the desired operating temperature and varied in the range 58-61 Nm3/h.
Due to heat loss from the relatively small pilot unit the adiabatic ATR exit temperature will be higher than the temperature given in Table 3. This means that if a large unit, frcrr. which the heat loss is negligible, is subjected to exact the same conditions, the ATR exit temperature will be close to the adiabatic ATR exit temperature.
Table 3
Figure imgf000007_0001
The composition of the product gas from the ATR reactor in the tests of Table 3 was measured by gaschromatography. Selected gas compositions are shown in Table 4. The gas composition is given as dry mole%, which is the mole composition of the gas components when steam is not included.
Table 4
Figure imgf000008_0001
The data in Table 3 clearly demonstrate the influence of the steam distribution on the critical steam to carbon ratio. The critical steam to carbon ratio is 44% higher in test number 1.1 than in test number 1.3. The steam concentration in the oxygen containing feed stream is 29% in test 1.1 and 5% in test 1.3. A similar but less pronounced influence is seen at higher temperature. The critical steam to carbon ratio is 15% higher in test number 2.1 than in test number 2.2, where the steam concentrations are 24% and 6% respectively in the oxygen containing stream.

Claims

1. Process for the preparation of a hydrogen and/or carbonmonoxide rich gas comprising the step of partial oxidation of a hydrocarbon feedstock with an oxygen containing reactant stream in presence of steam, wherein the steam is present in the hydrocarbon feedstock in an amount higher than in the oxygen containing reactant stream.
2. Process according to claim 1, wherein the partial oxidation step is performed in a burner arranged at top of an autothermal reactor.
3. Process according to claim 1, wherein less than 1/3 of the total steam feed is introduced with the oxygen containing stream.
4. Process according to claim 1, wherein the steam content of the oxygen containing feed stream is less than 12%.
AMENDED CLAIMS
[receveid by the International Bureau on 14 december 1999 (14.12.99); original ciaim 1 amended; remaining claims unchanged (lpage )]
1. Process for the preparation of a hydrogen and/or carbonmonαxiάa rich gas comprising εhe step of partial oxidation of s. hydrocarbon feedstock with an oxygen con- caining reaccan stream in presence of steam, wherein the steam is present in the hydrocarbon feedstock in an amount higher than i the oxygen containing reactant stream; with the proviso that the hydrocarbon feedstock is not a primary reformed gas.
2. process according to claim, i, wherein the partial oxidation step is performed in a burner arranged at top of an autothermal reactor.
3. Process according to claim l, wherein less than 1/3 of the total steam feed is introduced with the oxygen containing stream.
4. Process according to claim 1, wherein the steam content of the oxygen containing feed stream is less than 12%.
STATEMENT UNDER ARTICLE 19
Submitted herewith in triplicate are new claims 1 to 4 which are to replace original claims 1 to 4.
New claim 1 is based on original claim 1 further including the disclaimer that the hydrocarbon feedstock is not a primary reformed gas.
New claims 2 to 4 correspond to original claims 2 to 4.
PCT/EP1999/004561 1998-07-02 1999-07-01 Process for autothermal reforming of a hydrocarbon feedstock Ceased WO2000001613A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT99932778T ATE307778T1 (en) 1998-07-02 1999-07-01 METHOD FOR STEAM REFORMING A HYDROCARBON
DE69927976T DE69927976T2 (en) 1998-07-02 1999-07-01 METHOD FOR STEAM REFORMING A HYDROCARBON
JP2000558025A JP4154123B2 (en) 1998-07-02 1999-07-01 Method for automatic thermal reforming of hydrocarbon feedstocks
EP99932778A EP1098838B1 (en) 1998-07-02 1999-07-01 Process for autothermal reforming of a hydrocarbon feedstock
US09/720,652 US6689294B1 (en) 1998-07-02 1999-07-01 Process for autothermal reforming of a hydrocarbon feedstock
AU49044/99A AU754632B2 (en) 1998-07-02 1999-07-01 Process for autothermal reforming of a hydrocarbon feedstock
NO20006713A NO20006713L (en) 1998-07-02 2000-12-29 Process for autothermal reforming of a hydrocarbon solid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA199800897 1998-07-02
DKPA199800897 1998-07-02

Publications (1)

Publication Number Publication Date
WO2000001613A1 true WO2000001613A1 (en) 2000-01-13

Family

ID=8098778

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004561 Ceased WO2000001613A1 (en) 1998-07-02 1999-07-01 Process for autothermal reforming of a hydrocarbon feedstock

Country Status (11)

Country Link
US (1) US6689294B1 (en)
EP (1) EP1098838B1 (en)
JP (1) JP4154123B2 (en)
CN (1) CN1190356C (en)
AT (1) ATE307778T1 (en)
AU (1) AU754632B2 (en)
DE (1) DE69927976T2 (en)
ES (1) ES2251205T3 (en)
NO (1) NO20006713L (en)
WO (1) WO2000001613A1 (en)
ZA (1) ZA200007806B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178002A (en) * 1998-08-27 2000-06-27 Haldor Topsoe As Autothermal reforming of hydrocarbon feeds
US7989511B2 (en) 2008-05-21 2011-08-02 Texaco Inc. Process and apparatus for synthesis gas and hydrocarbon production
US8394154B2 (en) 2007-12-28 2013-03-12 Texaco Inc. Counter-current oxidation and steam methane reforming process and reactor therefor
WO2016198245A1 (en) * 2015-06-12 2016-12-15 Thyssenkrupp Industrial Solutions Ag Determining pressure, temperature and s/c ratio for soot-free atr operation
US11649163B2 (en) 2019-04-08 2023-05-16 Haldor Topsøe A/S Chemical synthesis plant
US12617679B2 (en) 2019-04-08 2026-05-05 Haldor Topsøe A/S Chemical synthesis plant

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001286258A1 (en) * 2000-09-20 2002-04-02 Teikoku Oil Co., Ltd Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane
US9637432B2 (en) * 2014-12-17 2017-05-02 Praxair Technology, Inc. Method and system for producing methanol using partial oxidation
EP3927656A4 (en) * 2019-02-18 2023-06-21 Skyre, Inc. METHOD AND SYSTEM FOR RECOVERING HYDROGEN AND CONVERTING A CARBON COMPOUND INTO A VALUABLE ORGANIC PRODUCT

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666680A (en) * 1984-01-30 1987-05-19 Fluor Corporation Autothermal production of synthesis gas
EP0307843A1 (en) * 1987-09-16 1989-03-22 Air Products And Chemicals, Inc. Production of hydrogen and carbon monoxide
US5358696A (en) * 1993-12-01 1994-10-25 Texaco Inc. Production of H2 -rich gas

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822521A (en) * 1983-06-09 1989-04-18 Uop Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons
DE3902773A1 (en) * 1989-01-31 1990-08-02 Basf Ag METHOD FOR PRODUCING SYNTHESIS GAS BY PARTIAL OXIDATION
DK168460B1 (en) * 1991-12-06 1994-03-28 Topsoe Haldor As Swirl burner
US5411927A (en) * 1992-08-14 1995-05-02 Council Of Scientific & Industrial Research Process of preparing composite catalysts for production of synthesis gas by oxidative conversion of methane or natural gas
EP0936182A3 (en) * 1998-02-13 2000-02-23 Haldor Topsoe A/S Method of soot-free start-up of autothermal reformers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666680A (en) * 1984-01-30 1987-05-19 Fluor Corporation Autothermal production of synthesis gas
EP0307843A1 (en) * 1987-09-16 1989-03-22 Air Products And Chemicals, Inc. Production of hydrogen and carbon monoxide
US5358696A (en) * 1993-12-01 1994-10-25 Texaco Inc. Production of H2 -rich gas

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178002A (en) * 1998-08-27 2000-06-27 Haldor Topsoe As Autothermal reforming of hydrocarbon feeds
EP0982266A3 (en) * 1998-08-27 2000-09-27 Haldor Topsoe A/S Process for autothermal reforming of a hydrocarbon feedstock
US8394154B2 (en) 2007-12-28 2013-03-12 Texaco Inc. Counter-current oxidation and steam methane reforming process and reactor therefor
US7989511B2 (en) 2008-05-21 2011-08-02 Texaco Inc. Process and apparatus for synthesis gas and hydrocarbon production
WO2016198245A1 (en) * 2015-06-12 2016-12-15 Thyssenkrupp Industrial Solutions Ag Determining pressure, temperature and s/c ratio for soot-free atr operation
US11649163B2 (en) 2019-04-08 2023-05-16 Haldor Topsøe A/S Chemical synthesis plant
US12180072B2 (en) 2019-04-08 2024-12-31 Haldor Topsøe A/S Chemical synthesis plant
US12617679B2 (en) 2019-04-08 2026-05-05 Haldor Topsøe A/S Chemical synthesis plant

Also Published As

Publication number Publication date
AU754632B2 (en) 2002-11-21
ES2251205T3 (en) 2006-04-16
DE69927976D1 (en) 2005-12-01
CN1311754A (en) 2001-09-05
ATE307778T1 (en) 2005-11-15
NO20006713L (en) 2001-03-02
ZA200007806B (en) 2002-05-02
US6689294B1 (en) 2004-02-10
NO20006713D0 (en) 2000-12-29
DE69927976T2 (en) 2006-04-20
AU4904499A (en) 2000-01-24
EP1098838A1 (en) 2001-05-16
EP1098838B1 (en) 2005-10-26
JP4154123B2 (en) 2008-09-24
CN1190356C (en) 2005-02-23
JP2002519293A (en) 2002-07-02

Similar Documents

Publication Publication Date Title
EP0989094B1 (en) Process for the autothermal reforming of a hydrocarbon feedstock containing higher hydrocarbons
US6527980B1 (en) Reforming with intermediate reactant injection
US8388864B2 (en) Process and plant for producing synthesis gas
US6525104B2 (en) Steam reforming
US8137422B2 (en) Steam-hydrocarbon reforming with reduced carbon dioxide emissions
EP2464598B1 (en) Combined reforming process for methanol production
NZ227799A (en) Process for the production of methanol
US6143202A (en) Process for the autothermal steam reforming of a hydrocarbon feedstock
EP1277721A2 (en) Method of manufacturing methanol
EA006869B1 (en) Production of hydrocarbons
EP1188713A2 (en) Production of hydrogen and carbon monoxide containing synthesis gas by partial oxidation
EP2142467A1 (en) Combined reforming process for methanol production
EP1098838A1 (en) Process for autothermal reforming of a hydrocarbon feedstock
AU2005306866A1 (en) Steam methane reforming method
EP0982266A2 (en) Process for autothermal reforming of a hydrocarbon feedstock
MXPA01000098A (en) Process for autothermal reforming of a hydrocarbon feedstock
EP4385947A1 (en) Decarbonisation of a chemical plant
GB2299341A (en) Raw synthesis gas

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99809159.6

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2000/07806

Country of ref document: ZA

Ref document number: 200007806

Country of ref document: ZA

ENP Entry into the national phase

Ref document number: 2000 558025

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 49044/99

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2000/00465/DE

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/000098

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1999932778

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09720652

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999932778

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWG Wipo information: grant in national office

Ref document number: 49044/99

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 1999932778

Country of ref document: EP