CA2091748A1 - Process for producing a hydrogen-containing gas - Google Patents

Process for producing a hydrogen-containing gas

Info

Publication number
CA2091748A1
CA2091748A1 CA 2091748 CA2091748A CA2091748A1 CA 2091748 A1 CA2091748 A1 CA 2091748A1 CA 2091748 CA2091748 CA 2091748 CA 2091748 A CA2091748 A CA 2091748A CA 2091748 A1 CA2091748 A1 CA 2091748A1
Authority
CA
Canada
Prior art keywords
gas
hydrocarbon
solids
containing gas
hydrogen
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.)
Abandoned
Application number
CA 2091748
Other languages
French (fr)
Inventor
Jelle Jacob Bakker
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.)
Shell Canada Ltd
Original Assignee
Shell Canada 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 Shell Canada Ltd filed Critical Shell Canada Ltd
Publication of CA2091748A1 publication Critical patent/CA2091748A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons

Abstract

A B S T R A C T

PROCESS FOR PRODUCING A HYDROGEN-CONTAINING GAS

A non-catalytic process for production of gases essentially comprising hydrogen and/or carbon monoxide from hydrocarbon-containing gases by contacting the latter gases with a bed of solids, with endothermic hydrocarbon cracking and/or water gas reaction steps by alternating combinations of exothermic and endothermic reactions via said solids. The hydrocarbon-containing gases are flash-heated to the desired reaction temperature of 950-1200 °C.

Description

20917~8 PROCESS FOR PRODUCING A HYDROGEN-CONTAINING GAS

The present invention relates to a non-catalytic process for producing a hydrogen-containing gas, wherein use is made of direct heat exchange via high temperature heat storage in refractories.
In particular, the invention relates to a non-catalytic process for producing a hydrogen-containing gas and/or synthesis gas from gaseous hydrocarbons such as e.g. methane, natural gas, associated gas, (i.e. gas produced together with oil in production fields), naphtha etc. in regenerator-type reactors. In such reactors which comprise heated solids, alternating combinations of exothermic and endothermic reactions are carried out in such a manner that the desired reactions:
CH4 > C + 2H2 and/or C + H2O - > CO + H2 and/or CH + H O > CO + 3H
will occur.
However, when using regenerator-type reactors for the production of hydrogen-containing gases, one is faced with the problem that the hydrocarbon-containing feed gases have to be heated to the desired reaction temperature of 1000-1200 C.
However, above a temperature of 400-600 C cracking of the hydrocarbon-containing feed gases will start leading to the formation of tarry and sooty material which is interfering with the desired process conditions through plugging of the equipment applied.
Thus, it is an object of the invention to provide a process for production of a hydrogen-containing gas from hydrocarbon-containing gases using a regenerator-type reactor, wherein the above problems are avoided.
The invention therefore provides a non-catalytic process for production of gas essentially comprising hydrogen and/or carbon monoxide from hydrocarbon-containing gas by contacting the latter - 2 - 209~7~
gas in a regenerator-type reactor with a bed of solids with endothermic hydrocarbon cracking and/or water gas reaction steps, by alternating combinations of exothermic and endothermic reactions vi.a said solids in regenerator-type reactors, characterized in that the hydrocarbon-containing gas is flash-heated to the desired reaction temperature of 950-1200 C.
Flash heating is herein defined as a process in which relative cold gases are heated in a very short time by mixing with very hot gases.
The invention will now be described by way of example in more detail by reference to the accompanying drawings, in which: Fig. 1 represents schematically the principle of the invention; and Figs. 2a, b represent schematically an advantageous application of the process of the present invention.
Referring now to Fig. 1, a regenerator-type reaction stove 1 is shown, in which stove the endothermic and exothermic reactions described in the foregoing are carried out.
Regenerator-type stoves as such are known to those skilled in the art from e.g. blast furnaces and will therefore not be described in detail.
Generally, it can be said that such a stove is a vessel comprising a bed of solids which are alternately heated up and cooled down, dependent on whether exothermic or endothermic reactions are carried out.
Advantageously the stove is largely filled with a "checker"
work consisting of stacked high temperature resistant refractory bricks with holes in them through which the gases flow. The stoves are operated in two cycles. For blast furnaces hot flue gases heat the checker in downflow. During the heating cycle and during the cooling cycle the checker in turn heats the upward flow of air for the blast furnace. During this cycle the stove is operated at the pressure of 3-S bar. By a proper sequence control the temperature of the air is held constant at 1290-1320 ~C.
The process according to the invention is suitably carried out in one or more fixed beds comprising a heated mass of solids. Fixed ~091748 beds could be applied which may contain heat-resistant solid material in any desired shape and size, such as a fixed brick matrix or a packed bed of particulate solids. Particulate solids such as packed spheres or cylinders with main dimensions ~e.g.
diameter, height of the cylinder) of 1-50 mm, and in particular 2-50 mm, are suitably used in the present process.
Various solid materials may be used in the process according to the present invention provided that the material is sufficiently heat-resistant and can withstand large temperature variations which occur during start-up and shut-down of the process. Suitable solids comprise refractory oxides, silicium carbide, carbonaceous materials (e.g. petrol cokes) and mixtures thereof. Metal alloys or metal compounds may also be suitably used; these materials have the advantage of possessing a relatively high thermal conductivity and volumetric heat capacity compared with the previously mentioned materials. In some cases it may be advantageous to use solids which, as such or in the form of additional compounds, possess catalytic activity for at least one of the process steps. However, in most cases substantlally non-catalytic solids will be most suited for use in the process according to the invention because the deposition of carbon on the surface of the solids will usually lead to a substantial decrease in catalytic activity, if present in fresh solids. Advantageously, the bed of solids comprises alumina beads.
Preheating of the solids applied in the process according to the invention to any temperature suitable for the purpose may be carried out in various ways. Advantageously, the solids are preheated to a temperature of 1400-1650 C before being contacted with the hydrocarbon-containing gas. Suitably the solids are heated by combustion under pressure of a fuel gas with an oxygen-containing gas and contacting the combustion gas with the solids, whereafter the combustion gas is cooled e.g. by preheating the hydrocarbon-containing gas and/or air.
Various gaseous hydrocarbonaceous materials can be used as feed for the process according to the invention. In particular 2~91~8 natural gas. methane, associated gas, LPG and evaporated naphtha ar.e used. In some cases natural gas is preferably subjected to a treatment to remove sulphur and/or inorganic substances before using it as feed for the present process.
Via an inlet la at the top of the stove l hydrocarbon-containing feed gases which usually are preheated from ambient temperature to 500 C in an indirect heat exchanger (not shown for reasons of clarity), are introduced into the stove l through any line 2 suitable for the purpose and an ejector-type compressor 3, which ensures rapid mixing and is suitable to be applied in a hot environment. Such compressors are known to those skilled in the art and will not be described in detail.
The product gas is discharged from the stove 2 via any suitable outlet lb at the bottom and any line 4 suitable for the purpose for further suitable processing.
After starting the process by heating the stove in any suitable manner, the gaseous hydrocarbons are flash-heated through the disadvantageous temperature zone to a temperature range where the above desired endothermic reactions occur, by recycling at least part of the hot product gases through any suitable recycle line 5 to the feed line 2 and the compressor 3, so that a reaction mixture comprising feed gases and hot recycled product gas is supplied to the inlet la.
The following non-limiting Example can be referred to: a quantity of 214.2 Ton/hr of hydrocarbon-containing feed gas is supplied to the compressor 3 via the feed line 2 at a temperature of 500 C and at a pressure of 11 bar.
When recycling, 547.0 Ton/hr of gaseous hydrocarbons are supplied from the compressor 3 to the inlet la at lO00 C and a pressure of 7.50 bar, whereas 547.0 Ton/hr of hot product gas at 1281 C and 7.47 bar is discharged from the outlet lb and subsequently is splitted into 332.8 Ton/hr of recycled gas at 1281 C in line 5 and 214.2 Ton/hr of product gas at 1281 C and 7.47 bar in line 4.

An additional advantage of the above line up is that the temperature profile in the stove can be controlled within narrow ranges. In this way problems as too low cut off temperatures during the heating of the stove can be avoided.
Figs. 2a and b represent block schemes of an advantageous embodiment of the invention wherein for heating of the reaction stove(s) use is made of a flue gas heat recovery stove as used in e.g. glass ovens. Such heat recovery stove are operating in a cyclic manner similar to that described earlier with respect to the blast furnace-type reactor. The process sequence is then as follows. In Fig. 2a (representing the heating cycle) combustion air supplied via any suitable line 6 to a heat recovery stove (A) is preheated in the heat recovery stove (A) to about 1000 C. By burning some fuel gas such as hydrogen supplied via any suitable line 2 to the reaction stove 1 with this air a flue gas is formed with a temperature of 1300 C which is used for heating the reaction stove 1. After the top heat between e.g. 1000 C and 1300 C has been used for heating the reaction stove 1 the remaining heat in the flue gas is used to preheat a second heat recovery stove (B). In the cooling cycle the said heat between 1000 C and 1300 C is then used to accomplish the endothermic reforming reactions leading to cooling down the stove, after which the reaction stove 1 is heated again in a heating cycle during which procedure the combustion air is heated in stove (B) and stove (A) is heated with the flue gas leaving the reaction stove 1 etc.
(see Fig. 2b).
Reference number 7 represents the flue gas to the stack from the second preheated heat recovery stove. In Figs. 2a and b the same reference numerals have been used.
To those skilled in the art it will be clear that in order to obtain a continuous flow of product gas at least two reaction stoves are required and at least 2 heat recovery stoves. Proper sequencing will then result in a more or less continuous flow of product gas, flue gas and preheated combustion air.

209~748 Various modifications of the present invention will become apparent to those skilled in the art from the foregoing description. Such modifications are intended to fall within the scope of the appended claims.

Claims (8)

1. A non-catalytic process for production of gas essentially comprising hydrogen and/or carbon monoxide from hydrocarbon-containing gas by contacting the latter gas in a regenerator-type reactor with a bed of solids, with endothermic hydrocarbon cracking and/or water gas reaction steps, by alternating combinations of exothermic and endothermic reactions via said solids in regenerator-type reactors characterized in that the hydrocarbon-containing gas is flash-heated to the desired reaction temperature of 950-1200 °C.
2. The process as claimed in claim 1, characterized in that the flash-heating is accomplished by contacting the hydrocarbon-containing gas at a temperature between 400 and 600 °C with at least part of the hot product gas having a temperature above 1200 °C.
3. The process as claimed in claim 2, characterized in that at least part of the hot product gas is recycled to the regenerator-type reactor.
4. The process as claimed in claim 3, characterized in that the hot product gas recycling takes place via an ejector-type compressor.
5. The process as claimed in any one of claims 1-4, characterized in that the hydrocarbon-containing gas is chosen from methane, natural gas, associated gas, or naphtha.
6. The process as claimed in any one of claims 1-5, characterized in that the bed of solids is heated by means of one or more flue gas heat recovery stoves.
7. Hydrogen-containing gas whenever obtained by the process as claimed in any one of claims 1-6.
8. Carbon monoxide-containing gas whenever obtained by the process as claimed in any one of claims 1-6.
CA 2091748 1992-03-23 1993-03-16 Process for producing a hydrogen-containing gas Abandoned CA2091748A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92200833 1992-03-23
EP92200833.9 1992-03-23

Publications (1)

Publication Number Publication Date
CA2091748A1 true CA2091748A1 (en) 1993-09-24

Family

ID=8210499

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2091748 Abandoned CA2091748A1 (en) 1992-03-23 1993-03-16 Process for producing a hydrogen-containing gas

Country Status (2)

Country Link
CA (1) CA2091748A1 (en)
GB (1) GB2265380B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491250B2 (en) 2002-06-25 2009-02-17 Exxonmobil Research And Engineering Company Pressure swing reforming
US6818198B2 (en) * 2002-09-23 2004-11-16 Kellogg Brown & Root, Inc. Hydrogen enrichment scheme for autothermal reforming
US7217303B2 (en) 2003-02-28 2007-05-15 Exxonmobil Research And Engineering Company Pressure swing reforming for fuel cell systems
US7914764B2 (en) 2003-02-28 2011-03-29 Exxonmobil Research And Engineering Company Hydrogen manufacture using pressure swing reforming
GB0314813D0 (en) * 2003-06-25 2003-07-30 Johnson Matthey Plc Reforming process
US7846401B2 (en) 2005-12-23 2010-12-07 Exxonmobil Research And Engineering Company Controlled combustion for regenerative reactors
US7608129B2 (en) * 2006-04-24 2009-10-27 Hyl Technologies S.A. De C.V. Method and apparatus for producing direct reduced iron
DE102012010542A1 (en) * 2011-12-20 2013-06-20 CCP Technology GmbH METHOD AND APPARATUS FOR GENERATING SYNTHESEGAS

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS523359B1 (en) * 1971-07-08 1977-01-27
JPS5315474B2 (en) * 1972-11-06 1978-05-25
GB8524894D0 (en) * 1985-10-09 1985-11-13 Shell Int Research Producing hydrogen-containing gas

Also Published As

Publication number Publication date
GB2265380B (en) 1996-01-17
GB9305909D0 (en) 1993-05-12
GB2265380A (en) 1993-09-29

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