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GB2222533A - Combined tubular primary and secondary reformer - Google Patents

Combined tubular primary and secondary reformer Download PDF

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Publication number
GB2222533A
GB2222533A GB8809319A GB8809319A GB2222533A GB 2222533 A GB2222533 A GB 2222533A GB 8809319 A GB8809319 A GB 8809319A GB 8809319 A GB8809319 A GB 8809319A GB 2222533 A GB2222533 A GB 2222533A
Authority
GB
United Kingdom
Prior art keywords
tube
oxidant
gas
reformer
reforming
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.)
Withdrawn
Application number
GB8809319A
Other versions
GB8809319D0 (en
Inventor
Frank Clifford Brown
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.)
Humphreys and Glasgow Ltd
Original Assignee
Humphreys and Glasgow Ltd
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 Humphreys and Glasgow Ltd filed Critical Humphreys and Glasgow Ltd
Priority to GB8809319A priority Critical patent/GB2222533A/en
Publication of GB8809319D0 publication Critical patent/GB8809319D0/en
Publication of GB2222533A publication Critical patent/GB2222533A/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • C01B3/384—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 the catalyst being continuously externally heated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00477—Controlling the temperature by thermal insulation means
    • B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam 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
    • C01B2203/025—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
    • C01B2203/06—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
    • C01B2203/08—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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • 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
    • 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
    • C01B2203/14—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
    • C01B2203/80—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A tubular reformer the first part of which is used for reforming of a pressurised steam/hydrocarbon mixture, and in the second part of which is oxidant is introduced directly into the tube, the oxidant then continues the catalytic reforming of the gas in the tube by virtue of the heat released by partial oxidation of part of the gas; the hot reformed gas leaving the tube is then used to heat the reactants inside the tube. <IMAGE>

Description

DESIGN FOR A COMBINED TUBULAR PRIMARY AND SECONDARY REFORMER This invention is a combined tubular primary and secondary reformer in which heat from the oxidation of part of the feedstock is used to partially preheat and reform all or part of a hydrocarbon and steam mixture fed to the reformer.
There now follows a description of one embodiment of the invention.
Steam and hydrocarbon are preheated externally to the reformer. The hot gas then flows from the top head of the reformer down through an annul us inside a tube the annul us being filled with an appropriate commercially available steam/hydrocarbon reforming catalyst-generally nickel supported on a refractory material. The ratio of steam to hydrocarbon is in the molar range 1.0:1 to 4.5:1, more likely in the range 2.0 - 2.5:1. At the entry to the tube it is at a temperature of between 350 and 600 C more likely 500 - 600 C.
As the gas flows down the tube it is heated by hot reformed gas flowing outside the tube and is partly reformed. Some distance down the tube the catalyst is changed to a combined combustion and reforming catalyst. Shortly after this change an inner pipe discharges oxidant into the catalyst-filled annul us through a series of holes. As the oxidant meets the partially reformed gas partial oxidation takes place resulting in heat release and further reforming.
At the exit of the tube reforming is complete and the gas leaves the tube at a temperature between 600 and 1500 C more likely in the range 800 to 1000 C.
The hot gas then flows upwards around the outside of the tube. The base of the tube, in the region of the combined combustion and reforming catalyst, may be insulated to maintain the temperature of the gas for the reforming sector. The reformed gas leaves the reformer close to the inlet gas tubesheet with a temperature within 150 C of the incoming hydrocarbon and more likely within 100 C.
It is possible to add further partially reformed gas at the base of the reformer. This will mix with the gas from the tubes and the heat from both streams can then be exchanged into the gas flowing in the tube-thus reducing on the quantity of oxidant required.
The oxidant is an oxygen-containing gas. Other compounds which may be present are nitrogen, steam and carbon dioxide. The operating pressure of the combined reformer is not limited but would usually be in the range 5 to 70 bar. More usually operation is likely to be in the range 25 - 55 bar. Since the differential pressure across the tube wall is low, the operating pressure has only a small effect on the mechanical design.
One embodiment of the mechanical design is shown in diagram 1.
Reformer tubes, in the size range 75 to 150 mm inside diameter, are connected at the top to a tube sheet and then fall vertically over a length of eg 10M to 20M. The tubes are arranged on a close pitch so as to increase the external heat transfer coefficient. The tube bundle is located in a refractory lined vessel which is either detachable at the tubesheet or at a flange lower down.
Above the tubesheet is an array of oxidant distributors arranged to allow catalyst loading and unloading. From the distributors the oxidant is led down the centre of the reforming tube in a small bore oxidant tube typically 15 - 40 mm OD. The top portion of the oxidant tube may be made of stainless steel containing less than 20% weight nickel. The lower portion of the oxidant tube, ie in the combustion region, may be made of either a high temperature nickel/chrome alloy, or a non metallic material such as silicon nitride. The catalyst support grid may also be made of non metallic material.
The reformer tube may be made of alloy material containing less than 20% nickel by weight for most applications. For very high temperatures at the outlet from the tube either a very high temperature alloy or a non metallic material like silicon nitride may be employed.
Example.
The following example is for the production of methanol synthesis gas.
For a reformer of between 6 to 10 tubes to produce ca 72 tonnes/day of methanol: Feed to tubes 100 kgmol/hr Methane and 250 kgmol/hr steam at 550 C and 33 bar Oxidant 48 kgmol/hr oxygen and 48 kgmol/hr steam at 220 C and 33 bar The product gas leaves the reactor at 650 C and 30 bar. The gas condition at the exit of the two catalyst stages are as follows: : Units Exit Exit Combustion Reforming Reforming Catalyst Catalyst Hydrogen kgmol/hr 93.9 236.6 Carbon monoxide kgmol/hr 4.4 56.0 Carbon dioxide kgmol/hr 20.2 , 41.1 Methane kgmol/hr 75.4 2.8 Steam kgmol/hr 205.2 255.7 Total kgmol/hr 399.1 592.2 Temperature C 635 937 Heat transferred to tube 1.6 Gcal/hr The invention is thus a tubular reformer the first part of which is used for reforming of a pressurised steam/hydrocarbon mixture, and in the second part of which an oxidant is introduced directly into the tube, the oxidant then continues the catalytic reforming of the gas in the tube by virtue of the heat released by partial oxidation of part of the gas; the hot reformed gas leaving the tube is then used to heat the reactants inside the tube.

Claims (1)

  1. COMBINED TUBULAR Claim 1 A tubular reformer the first part of which is used for reforming of a pressurised steam/hydrocarbon mixture, and in the second part of which oxidant is introduced directly into the tube, the oxidant then continues the catalytic reforming of the gas in the tube by virtue of the heat released by partial oxidation of part of the gas; the hot reformed gas leaving the tube is then used to heat the reactants inside the tube.
    Claim 2 A reformer as claimed in claim 1 wherein the gas leaving the tube is mixed with additional hot gas which has been reformed elsewhere.
    Claim 3 A reformer as claimed in claim 1 or 2 where a metal, containing less than 20% nickel (by weight), is used for the reforming tube, and the oxidant tube above the point where the oxidant flows through the holes in the oxidant tube.
GB8809319A 1988-04-20 1988-04-20 Combined tubular primary and secondary reformer Withdrawn GB2222533A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8809319A GB2222533A (en) 1988-04-20 1988-04-20 Combined tubular primary and secondary reformer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8809319A GB2222533A (en) 1988-04-20 1988-04-20 Combined tubular primary and secondary reformer

Publications (2)

Publication Number Publication Date
GB8809319D0 GB8809319D0 (en) 1988-05-25
GB2222533A true GB2222533A (en) 1990-03-14

Family

ID=10635510

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8809319A Withdrawn GB2222533A (en) 1988-04-20 1988-04-20 Combined tubular primary and secondary reformer

Country Status (1)

Country Link
GB (1) GB2222533A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0579942A1 (en) * 1992-07-20 1994-01-26 STONE &amp; WEBSTER ENGINEERING CORPORATION Lined reformer tubes for high pressure reformer reactors
WO1998058874A1 (en) * 1997-06-24 1998-12-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method and device for reforming hydrocarbons autothermally
WO2001055027A1 (en) * 2000-01-25 2001-08-02 Imperial Chemical Industries Plc Steam reformer
GB2384195A (en) * 2001-10-22 2003-07-23 Lattice Intellectual Property Heat source in a reformation apparatus and method
FR2837810A1 (en) * 2002-03-28 2003-10-03 Bosch Gmbh Robert Reformer for electric vehicle fuel cells, passes heating flow through second reformer countercurrent to hydrocarbon-containing flow

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2153382A (en) * 1984-01-30 1985-08-21 Fluor Corp Autothermal production of synthesis gas
GB2199841A (en) * 1983-06-09 1988-07-20 Union Carbide Corp Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2199841A (en) * 1983-06-09 1988-07-20 Union Carbide Corp Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons
GB2153382A (en) * 1984-01-30 1985-08-21 Fluor Corp Autothermal production of synthesis gas

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0579942A1 (en) * 1992-07-20 1994-01-26 STONE &amp; WEBSTER ENGINEERING CORPORATION Lined reformer tubes for high pressure reformer reactors
WO1998058874A1 (en) * 1997-06-24 1998-12-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method and device for reforming hydrocarbons autothermally
WO2001055027A1 (en) * 2000-01-25 2001-08-02 Imperial Chemical Industries Plc Steam reformer
GB2384195A (en) * 2001-10-22 2003-07-23 Lattice Intellectual Property Heat source in a reformation apparatus and method
GB2384195B (en) * 2001-10-22 2005-08-24 Lattice Intellectual Property A method and apparatus for performing steam reforming
FR2837810A1 (en) * 2002-03-28 2003-10-03 Bosch Gmbh Robert Reformer for electric vehicle fuel cells, passes heating flow through second reformer countercurrent to hydrocarbon-containing flow

Also Published As

Publication number Publication date
GB8809319D0 (en) 1988-05-25

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