WO1998023709A1 - Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins - Google Patents

Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins Download PDF

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Publication number
WO1998023709A1
WO1998023709A1 PCT/US1996/019115 US9619115W WO9823709A1 WO 1998023709 A1 WO1998023709 A1 WO 1998023709A1 US 9619115 W US9619115 W US 9619115W WO 9823709 A1 WO9823709 A1 WO 9823709A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
carbon
molten metal
feed
bath
Prior art date
Application number
PCT/US1996/019115
Other languages
English (en)
Inventor
Donald P. Malone
Original Assignee
Ashland Inc.
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 Ashland Inc. filed Critical Ashland Inc.
Priority to US09/308,530 priority Critical patent/US6254652B1/en
Priority to PCT/US1996/019115 priority patent/WO1998023709A1/fr
Priority to AU14074/97A priority patent/AU1407497A/en
Publication of WO1998023709A1 publication Critical patent/WO1998023709A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/57—Gasification using molten salts or metals

Definitions

  • the present invention relates to the use of molten metal baths to treat waste streams, coal, garbage and the like.
  • coal is such a difficult feed
  • the present invention is not limited to coal conversion.
  • Coal perhaps the most difficult fuel to process rather than bum, provides a good limiting case study on hydrogen deficient feeds, so a review of coal conversion art is instructive. This is followed by a review of art at producing hydrogen from clean fuels such as methane.
  • molten metal processing of these hydrogen- deficient, e.g., coal, and hydrogen-rich, e.g., methane, feeds cause problems.
  • Coal can be converted at great expense to form valuable clean fuels or at lesser expense to cheap, dirty fuels.
  • the high expense route to clean fuels involves gasification followed by Fischer Tropsch synthesis. This approach works, and has been used commercially by those countries without a secure source of oil .
  • the use of coal to form water gas or other low grade fuel which can be burned (with much of the contaminants still in the gas) is a low tech, environmentally unsuitable way to get a gaseous fuel from a difficult solid.
  • One promising new approach is use of molten metal baths to process coal. Coal dissolution is rapid. Ashland, if present, will form slag. The slag must be removed but, at least, the Ashland does not clog filters or slow coal processing. Hydrogen in the coal is rapidly released as hydrogen and usually just as rapidly burned because oxygen addition usually proceeds in lock step with carbon burning, and in the same bath of molten metal receiving coal.
  • molten metal processing of clean fuels produces hydrogen or, at least, a cleaner fuel gas, and some heat input (or hydrogen combustion) is needed for heat balance.
  • Clean light feeds such as methane
  • Hydrogen-deficient feeds such as coal potentially added very little hydrogen to the bath, but large amounts of carbon.
  • Patentees have devised several ways to overcome this problem, mixing light and heavy feed, or adding CO or steam to the oxidizing side to promote other reactions which would keep things in heat balance. While these approaches helped to a considerable extent, they all were somewhat restrictive in practice. If a refiner, or waste processor, had to dispose of some asphaltic feed, the "mixing" solution would make the feed lighter (or richer in hydrogen) by adding some lighter material such as methane. The methane/asphaltic "blend” would then be processed in the molten metal reactor, yielding a hydrogen product stream of intermediate purity. The hydrogen would be purer than could be obtained when processing an asphalt feedstock, but not as pure as when processing a methane feedstock.
  • the hydrogen content in the gas produced in each dissociation zone is primarily indicative of the feed properties to each zone, while the carbon level increases slowly (for methane) or quickly (for SDA bottoms).
  • the net amount of carbon added by both zones was appropriate for the amount of coke burned out of the molten metal bath in the oxidation zone.
  • Wlien practiced in a multi-bed, e.g., three-bed unit the feed and product lines associated with each zone will periodically shift from feed 1 , to feed 2 to an oxidant.
  • the present invention provides a heat balanced, molten metal process for sequentially converting at least two different feedstocks, a hydrogen rich feed having a carbon: hydrogen mole ratio no greater than 1 and a hydrogen deficient feed having a carbon:hydrogen mole ratio greater than that of said hydrogen rich feed, in a single molten metal bath to produce at least two product vapor streams comprising heating a molten metal bath containing dissolved carbon by adding oxygen or an oxygen containing gas at an oxygen gas rate to said bath and exothennically oxidizing in said bath at least a portion of said dissolved carbon to produce a carbon oxide gas product which is removed as a product stream from said reactor; cooling said molten mctal bath by sequentially thermally converting in said bath, in any order, both said hydrogen rich feed, in the absence of added oxygen, to produce a high purity, at least 90 - mole % hydrogen, hydrogen gas product which is removed as a product stream from said reactor and carbon which dissolves in
  • the present invention provides a heat balanced, molten metal process for sequentially converting a hydrogen rich feed comprising a distillable or normally gaseous hydrocarbon to essentially pure hydrogen and a hydrogen deficient feed comprising a carbon containing solid or a non-distillable hydrocarbon liquid to a low hydrogen content vapor product in a single molten metal bath comprising heating a molten metal bath containing dissolved carbon by adding oxygen or an oxygen containing gas at an oxygen gas rate to said bath and exothennically oxidizing in said bath at least a portion of said dissolved carbon to produce a carbon oxide gas product with a H 2 :CO ratio below 1 .0, molar basis, which is removed as a product stream from said reactor; processing sequentially in said bath and thenrially converting, in any order, both said hydrogen rich feed, in the absence of added oxygen, to produce at least 98 + mole % hydrogen, hydrogen gas product which is removed as a product stream from said reactor and carbon which dissolves in said mol
  • Figure 2 is a plot of the percent purity of hydrogen product gas versus time for the swing system of Figure 1 .
  • Figure 3 is an exploded, perspective view of Figure 1 .
  • Figure 4 is a more detailed sectional view of a molten metal reactor in an alloy pressure vessel with rammed thennal insulation.
  • Natural Gas (CH 4 ), liquefied petroleum gas (LPG), propane, petroleum naphtha, light or heavy distillate.
  • LPG liquefied petroleum gas
  • propane propane
  • petroleum naphtha propane
  • light or heavy distillate Normally gaseous hydrocarbons are preferred.
  • ethane and methane which can produce substantially pure hydrogen.
  • HYDROGEN DEFICIENT FEED MATERIALS Vacuum and other resids, solvent deasphalted pitch (SDA), aromatic extracts, FCC slurry oil, trash, garbage, tires, coal, virtually any other hydrocarbon-containing material. Many of these materials have significant amounts of hydrogen, but for purposes of the present invention they may be considered hydrogen deficient.
  • Preferred low hydrogen content feeds are solvent deasphalter (SDA) bottoms, residuum from the vacuum distillation tower and coal. Petroleum coke, a suitable feed, has about a 0.1 : 1 H:C ratio.
  • PRODUCTS The process will always produce a pure hydrogen product and in addition one or more products of significantly lower purity.
  • the hydrogen, or clean fuel product is reviewed first, followed by a review of the reduced hydrogen purity product, or dirty fuel product, and flue gas product.
  • H 2 rich feed can produce extremely pure industrial hydrogen, generally with a hydrogen purity in excess of 90 mole %, and preferably in excess of 95, 98 or even 99 mole %. If clean, light feeds are used, and if the rest of the process is operated properly, the vapor product will have few impurities, perhaps a minor amount, usually less than 1 mole % of H 2 S. This vapor stream might properly be labeled the "clean fuel" product.
  • the process To get more fuel in the bath, the process must operate for a time with a carbon- rich, hydrogen-deficient feed. During this period of operation, relatively large amounts of carbon are added to the metal bath, releasing a vapor product that might be tenned a "dirty fuel". Products are H 2 , plus H 2 S and other contaminants in feed.
  • FLUE GAS During carbon oxidation, the off-gas will also contain CO and/or C0 2 . This material may have significant combustion potential, especially if much of the product of carbon combustion is carbon monoxide rather than carbon dioxide.
  • CONTROLS Conventional analog or digital controls may be used, measuring temperature, preferably with optical or infrared pyrometer or protected thennocouple; carbon by spectrometers; level by nuclear radiation and adjusting reflective amounts of feed to maintain temperature. Temperature of the molten metal is preferably 1150°C to
  • Reactor temperature drops quickly during addition of H 2 rich feed, usually more slowly during addition of the H 2 deficient feed, and increases with oxygen addition. Reactor temperature may swing 25° to
  • the swing can be controlled on the basis of elapsed time, mass fed, percent carbon in molten metal, product purity, or other variables.
  • the process of the present invention can work well at atmospheric pressure.
  • the hydrogen product is much more valuable if produced at a pressure of at least 2 atm., absolute, and preferably at 5 atm., absolute or higher. It is possible to run every sequence of the process at superatmospheric pressure, or to run only the clean fuel (high purity H2) part at high pressure with the carbon burn step operated at lower pressure, or at atmospheric pressure.
  • the present invention can work well using a simple, single chamber reactor or crucible containing molten metal.
  • This reactor is sequentially fed two different hydrocarbon feeds to produce product gas with varying hydrogen purities and preferably an oxygen-containing gas to produce carbon monoxide and/or dioxide.
  • the invention can use a swing valving sequence which connects the reactor to a high purity hydrogen header for collecting pure hydrogen , and one or more dirty fuel gas headers. Swing valves are preferably located downstream of product heat-exchangers for lower temperature operation.
  • a vent may purge gas lines during feed transition periods. Minimum dissolved carbon level during occasional carbon oxidation cycles may be further reduced to periodically oxidize any sulfur in the melt and metals such as vanadium. Vanadium may be periodically purged from the melt by oxidation.
  • Table A summarizes preferred, more preferred and most preferred parameters of the process of the invention.
  • FIG 1 shows schematically a swing valve system for molten metal reactor 10 receiving H 2 rich feed in line 14 and H 2 deficient hydrocarbon feed source 16, in this case (SDA). Each cycle is reviewed seriatim.
  • the SDA pitch in line 16 is fed first to reactor 10 through inlet valve 20 and
  • Lance 30 is insulated
  • CARBON BURN CYCLE After a preset time, about three minutes in this example, feed addition is
  • a mix of CO/C0 2 is removed through valve 95.
  • vapors may be vented via line 140 and valve 146 between some or
  • Crucible 2 ( Figure 3) shows a pressure-tight steel housing 4, with
  • feeds one hydrogen rich and one hydrogen deficient
  • Three mode operation is preferred. It involves sequencing the reactor
  • a carbon bum cycle is always needed to generate the heat needed to drive the
  • the reactor must be heated enough in the carbon burn cycle to remain
  • the viscosity of the molten bath changes both with temperature and with carbon
  • the reactor should not be operated so near "the edge” that minor
  • a swing of about 150°-200°C, from say 1250°-l450°C provides a
  • carbon level may be set by needs to maintain a more reducing atmosphere in a
  • the carbon content is at least 50 % removed during the carbon burn cycle.
  • the bed should contain less than 2.0 wt.% carbon, preferably less than 1.5 wt.%
  • the oxidant used to remove carbon is preferably pure oxygen, though oxygen
  • enriched air or other oxygen containing stream may also be used.
  • the gas removed from the bed during the oxidation part of the cycle will usually contain large amounts
  • the H 2 rich feed will be processed after decarbonization of the
  • the molten metal bath will be clean and hot. High temperatures will rapidly
  • the reactor still processes two different feeds, and still
  • hydrogen is used in a hydrotreater or the like.
  • the process of the present invention uses the molten metal bath as
  • the molten metal bath handles two swings, temperature and composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

Il est procédé à un traitement séquentiel d'alimentations riches (14) et pauvres (16) en hydrogène, dans un seul bain de métal liquide (40), thermiquement équilibré, pour produire, à la fois, 90 et plus en pourcentage molaire d'hydrogène et un courant de vapeur, sinon plusieurs, à faible niveau de pureté (140). Le bain de métal liquide est réchauffé par adjonction d'oxygène (18) afin de brûler le carbone dissous dans le bain, puis refroidi par adjonction séquentielle de deux alimentations à teneurs différentes en hydrogène. On obtient, de préférence, un hydrogène à 98 % sous une pression absolue de deux atmosphères au moins ainsi qu'un courant contenant de l'hydrogène à faible niveau de pureté et un courant distinct de gaz de combustion d'oxydes de carbone.
PCT/US1996/019115 1995-04-13 1996-11-25 Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins WO1998023709A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/308,530 US6254652B1 (en) 1995-04-13 1996-11-25 At least three-step molten metal decomposition process cycle
PCT/US1996/019115 WO1998023709A1 (fr) 1996-11-25 1996-11-25 Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins
AU14074/97A AU1407497A (en) 1996-11-25 1996-11-25 At least three-zone molten metal decomposition process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/019115 WO1998023709A1 (fr) 1996-11-25 1996-11-25 Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins

Publications (1)

Publication Number Publication Date
WO1998023709A1 true WO1998023709A1 (fr) 1998-06-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/019115 WO1998023709A1 (fr) 1995-04-13 1996-11-25 Procede de decomposition a l'aide de metal liquide faisant intervenir trois zones au moins

Country Status (2)

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AU (1) AU1407497A (fr)
WO (1) WO1998023709A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4187672A (en) * 1977-11-17 1980-02-12 Rasor Associates, Inc. Apparatus for converting carbonaceous material into fuel gases and the recovery of energy therefrom
US4338096A (en) * 1980-10-06 1982-07-06 Cosden Technology, Inc. Method and apparatus for controlling the flow of molten reaction media
US4574714A (en) * 1984-11-08 1986-03-11 United States Steel Corporation Destruction of toxic chemicals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4187672A (en) * 1977-11-17 1980-02-12 Rasor Associates, Inc. Apparatus for converting carbonaceous material into fuel gases and the recovery of energy therefrom
US4338096A (en) * 1980-10-06 1982-07-06 Cosden Technology, Inc. Method and apparatus for controlling the flow of molten reaction media
US4574714A (en) * 1984-11-08 1986-03-11 United States Steel Corporation Destruction of toxic chemicals

Also Published As

Publication number Publication date
AU1407497A (en) 1998-06-22

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