CA2136074A1 - Method for treating organic waste - Google Patents
Method for treating organic wasteInfo
- Publication number
- CA2136074A1 CA2136074A1 CA002136074A CA2136074A CA2136074A1 CA 2136074 A1 CA2136074 A1 CA 2136074A1 CA 002136074 A CA002136074 A CA 002136074A CA 2136074 A CA2136074 A CA 2136074A CA 2136074 A1 CA2136074 A1 CA 2136074A1
- Authority
- CA
- Canada
- Prior art keywords
- molten metal
- carbon
- enriched
- organic waste
- gas stream
- 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
Links
- 239000010815 organic waste Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 139
- 239000002184 metal Substances 0.000 claims abstract description 139
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000007789 gas Substances 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000007800 oxidant agent Substances 0.000 claims abstract description 44
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 21
- 239000001569 carbon dioxide Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 150000002739 metals Chemical class 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 229910021398 atomic carbon Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229940099408 Oxidizing agent Drugs 0.000 description 33
- 229940105305 carbon monoxide Drugs 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000470 constituent Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- IJJWOSAXNHWBPR-HUBLWGQQSA-N 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]-n-(6-hydrazinyl-6-oxohexyl)pentanamide Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)NCCCCCC(=O)NN)SC[C@@H]21 IJJWOSAXNHWBPR-HUBLWGQQSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 241000357437 Mola Species 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- -1 butane Chemical compound 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/32—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or metals
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
2136074 9325277 PCTABS00028 A method is disclosed which relates to treating an organic waste containing hydrogen and carbon in molten metal contained in a vessel to sequentially form enriched hydrogen and carbon oxide gas streams. In one embodiment, the organic waste is introduced into molten metal, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize the molten metal. Thereafter, a separate oxidizing agent is added into the carbonized molten metal to oxidize the carbon contained in the carbonized molten metal to thereby generate an enriched carbon oxide gas stream and to decarbonize the molten metal.
Description
WO 93/25277 PCI/US93/05398 ~
METHOD FOR TREATING ORGANIC WASTE
Backqround of the Invention Disposal of organic wastes in landfills and by incineration has become an increasingly difficult ~
S problem because of diminishing availability of disposal -space, strengthened governmental regulations, and the growing public awareness of the impact of hazardous substance contamination upon the environment. Release of hazardous organic wastes to the environment can contaminate air and water supplies thereby diminishing the quality of life in the affected populations.
~ To minimize the environmental effects of the disposal of organic wastes, methods must be developed to convert these wastes into benign, and preferably, l5~ useful substances. In response to this need, there has been~a substantial investment in the development of : `
alternate methods for suitably treating hazardous organic wastes. One of the most promising new methods is described in U.S. Patents 4,574,714 and 4,602,574, ;~ 20 issued to Bach and Nagel. The Bach/Nagel method for destroying~organic material, including toxic wastes, involves decomposition of the organic material to its ~`
atomic constituents in a mo}ten metal and reformation of these atomic constituents into environmentally acceptable products, including hydrogen, carbon monoxide and/or carbon dioxide gases. ;
summarY of the Invention The present invention relates to a method for treating organic waste in molten metal contained in a :
, ,~ .
W093/25277 PCT/US93/053g8 ,-60rl~ `
~ ~.
METHOD FOR TREATING ORGANIC WASTE
Backqround of the Invention Disposal of organic wastes in landfills and by incineration has become an increasingly difficult ~
S problem because of diminishing availability of disposal -space, strengthened governmental regulations, and the growing public awareness of the impact of hazardous substance contamination upon the environment. Release of hazardous organic wastes to the environment can contaminate air and water supplies thereby diminishing the quality of life in the affected populations.
~ To minimize the environmental effects of the disposal of organic wastes, methods must be developed to convert these wastes into benign, and preferably, l5~ useful substances. In response to this need, there has been~a substantial investment in the development of : `
alternate methods for suitably treating hazardous organic wastes. One of the most promising new methods is described in U.S. Patents 4,574,714 and 4,602,574, ;~ 20 issued to Bach and Nagel. The Bach/Nagel method for destroying~organic material, including toxic wastes, involves decomposition of the organic material to its ~`
atomic constituents in a mo}ten metal and reformation of these atomic constituents into environmentally acceptable products, including hydrogen, carbon monoxide and/or carbon dioxide gases. ;
summarY of the Invention The present invention relates to a method for treating organic waste in molten metal contained in a :
, ,~ .
W093/25277 PCT/US93/053g8 ,-60rl~ `
~ ~.
-2-vessel to sequentially form enriched hydrogen gas ~nd carbon oxide gas streams.
In one embodiment, an organic waste containing hydrogen and carbon is introduced into molten metal, -without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize the molten metal. The enriched hydrogen gas stream is substantially removed from the 10 vessel. Thereafter, a separate oxidizing agent is I~Y
added into the carbonized molten metal to ox~idize ;
carbon contained in the carbonized molten metal to form ~`
an enriched carbon oxide gas stream. The enriched -carbon oxide gas stream is substantially removed from '~
the vessel.
In another embodiment of the invention employed to ~- increase the amount of carbon dioxide to carbon monoxlde in the enriched carbon oxide gas st~ream, the organic waste is introduced into molten meta~l contained -in a vessel which comprises two immiscible metals wherein the first immiscible metal h-as a free energy of oxidation, at the operating conditions, greater than that ~for axidation of carbon to carbon monoxide and the second~lmmiscible metal has a free energy o~ oxidation, at the operati~ng conditions~ greater ~than that for oxidation of carbon monoxide to carbon dioxide, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize at Ieast one of the two immiscible metals.
The enriched hydrogen gas stream is substantially ...',:
, ' W093/25t77 PCT/US93/05398 ~
607~ `;
.
:
,., . ~.,.
In one embodiment, an organic waste containing hydrogen and carbon is introduced into molten metal, -without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize the molten metal. The enriched hydrogen gas stream is substantially removed from the 10 vessel. Thereafter, a separate oxidizing agent is I~Y
added into the carbonized molten metal to ox~idize ;
carbon contained in the carbonized molten metal to form ~`
an enriched carbon oxide gas stream. The enriched -carbon oxide gas stream is substantially removed from '~
the vessel.
In another embodiment of the invention employed to ~- increase the amount of carbon dioxide to carbon monoxlde in the enriched carbon oxide gas st~ream, the organic waste is introduced into molten meta~l contained -in a vessel which comprises two immiscible metals wherein the first immiscible metal h-as a free energy of oxidation, at the operating conditions, greater than that ~for axidation of carbon to carbon monoxide and the second~lmmiscible metal has a free energy o~ oxidation, at the operati~ng conditions~ greater ~than that for oxidation of carbon monoxide to carbon dioxide, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize at Ieast one of the two immiscible metals.
The enriched hydrogen gas stream is substantially ...',:
, ' W093/25t77 PCT/US93/05398 ~
607~ `;
.
:
,., . ~.,.
-3- ;
removed from the vessel. Thereafter, a separate oxidizing agent is added into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to generate an enriched carbon monoxide and carbon dioxide gas stream having a significantly increased ratio of carbon dioxide/carbon monoxide ;--compared to that produced in molten iron under the same conditions and decarbonizing the molten metal. The ~
enriched carbon oxide gas stream is substantially `
removed from the vessel.
This invention has the advantage of treating -organic waste to form an enriched stream of hydrogen gas and a separate enriched stream of carbon oxide gas, such as carbon monoxide or carbon dioxide or both.
Enriched hydrogen and/or carbon oxide gas streams are often desired. For example, an enriched stream of -~
hydrogen gas is particularly useful in the synthesis of ~-`
ammonia or oxoalcohol and in hydrogenation or desulfurization processes. Hydrogen is also an excellent "clean" or "greenhouse gas free" fuel.
, Brief Descri~tion of the Drawinqs ;~
Figure 1 is a schematic representation of a system ;~
for sequentially forming enriched hydrogen and enriched carbon oxide gas streams from an organic waste in `~
25 molten metal by a method according to this invention. ``
Figure 2 is a plot of the free energies at varying -temperatures for the oxidation of nickel, iron and carbon.
W093/2s277 PCT/US93/05398 ,~.
601 ~ ~
Detailed Description of the Invention ~ , The features and other details of the method of the invention will now be more particularly described s with reference to the accompanying drawings and pointed 5 out in the claims. It will be understood that the particular embodiments of the invention are shown by way of illustration and not as limitations of the invention. The principle features of this invention can be employed in various embodiments without 10 departing from the scope of the invention.
The present invention generally relates to a method for treating organic waste in molten metal to separately form enriched hydrogen and carbon oxide gas streams. This invention is an improvement of the Bach/Nagel method disclosed in U.S. Patents 4,574,714 and 4,602,S74, the teachings of which are incorporated by reference.
One embodiment of the invention is illustrated in Figure 1. Therein, system 10 includes reactor 12.
Examples of suitable reactors include appropriately modified steelmaking vessels known in the art as K-BOP, Q-BOP, argon-oxygen decarbonization furnaces (AOD), BOF, etc. Reactor 12 includes upper portion 14 and lower portion 16. Off-gas outlet 18 extends from upper portion 14 and is suitable for conducting an off-gas composition out of reactor 12.
Organic waste inlet tube 20 includes organic material inlet 22 and extends from lower portion 16 of reactor 12. Line 24 extends between organic waste source 26 and organic waste inlet tube 20. Pump 28 is disposed in line 24 for directing organic waste from W093/2s277 PCT/US93/05398 213607~
, . .
organic waste source 26 through organic waste inlet .
tube 20 and into molten metal contained in reactor 12. `
Tuyere 30 is disposed at lower portion 16 of .
reactor 12. Tuyere 30 includes oxidizing agent tube 32 for injection of a separate oxidizing agent at oxidizing agent inlet 34. Line 36 extends between oxidizing agent tube 32 and oxidizing agent source 38.
Outer tube 40 of tuyere 30 is disposed concentrically about oxidizing agent tube 32 at oxidizing agent inlet :
34. Line 42 extends between outer tube 40 and shroud .
gas source 44 for conducting a suitable shroud gas from shroud gas source 44 through the ConcentFic opening -~
. between outer tube 40 and oxidizing agent tube 32 to .
oxidizing agent inlet 34. -~t is to be understood, however, that more than ~`
one organic waste tube or more than one oxidizing agent `~.
tube, or combinations thereof, can be disposed at the :~
lower portion of reactor 12 for introduction of organic ;`-.
waste and an oxidizing agent into reactor 12. Suitable organic waste can also, optionally, be introduced into reactor 12 through port 46 and/or conducted:from organic waste source 26 through line 47 to reactor 12. . ' Other means, such as an injection lance (not shown), t : can also be employed to introduce organic waste into molten metal in carbonization reactor 12.
Bottom tapping:spout 48 extends from lawer portion -16 of reactor 12 and is suitable for removal of molten ~.
metal from reactor 12.
Induction coil 50 is disposed at lower portion 16 - 30 for heating molten metal 56 in reactor 12. It is to be ~``
understood that, alternatively, reactor 12 can be ;-`.
W093/25277 PCT/US93/OS398 ~
2!L360~
.
heated by other suitable means, such as by oxy~uel burners, electric arcs, etc. -Trunions 52 are disposed at reàctor 12 for manipulation of reactor 12. Seal 54 is disposed 5 between off-gas outlet 18 and port 46 and is suitable --for allowing partial rotation of reactor 12 about trunions 52 without breaking seal 54. --Molten metal 56 is disposed within reactor 12. In one embodiment, molten metal 56 comprises a` metal having a free energy of oxidation, at operating conditions of system 10, which is greater than the free energy for conversion of atomic carbon to carbon -monoxide. Examples of suitable metals include iron, chromium and manganese. Molten metal 56 can include more than one metal. For example, molten metal 56 can include a solution of miscible metals, such as iron and chromium.
Suitable metals are those with melting points within the operating conditions of the system. It is preferred, for example, to run system 10 in a temperature range of from about 1300C to about 1700C.
-~ guitable metals must also have a carbon solubility sufficient to allow significant amounts of hydrogen to -be generated as organic waste is decomposed and the ;
25 molten metal becomes carbonized. Thus, metals with a ~
carbon solubility of greater than about 0.5 percent, by `
weight, are preferred, and those with a carbon solubility of greater than about two percent, by weight, are particularly preferred. In the cases where -more than one metal is employed, at least one of the : , `
W093/25277 PCT/US93/05398 ~-~ .
213607 ~
. .
. -metals should have the aforementioned carbon ~ -solubility.
In many cases, it is also preferred to have the viscosity of the molten metal in reactor 12 less than about ten centipoise at the operating conditions of reactor 12. -~
Molten metal 56 is formed by at least partially filling reactor 12 with a suitable metal. The metal is ~
then heated to a suitable temperature by activation of `
10 induction coil 52 or by other suitable means, not ;~
shown. Suitable operating conditions of system 10 include a temperature sufficient to at least partially `
convert organic waste by decomposition to hydrogen and i carbon. Generally, a temperature in the range of `
~etween about 1,300 and about 1,700C is suitable.
Optionally, molten metal 56 can have vitreous or slag layer 62. Vitreous layer 62, which is disposed on molten metal 56, is substantially immiscible with `
molten metal 56. Vitreous layer 62 can have a lower thermal conductivity than that of molten metal 56.
Radiant heat loss from molten metal 56 can thereby be reduced to significantly below the radiant heat loss -from molten bath where no vitreous layer is present.
Typically, a vitreous layer 62 includes at least 25 one metaI oxide having a free energy of oxidation, at `~
the operating conditions of system 10, which is less than that for the oxidation of atomic carbon to carbon monoxide, such as calcium oxide (CaO). Vitreous layer 62 can contain a suitable compound for scrubbing `-halogens, such as chlorine or fluorine, to prevent Wos3t2s277 PCT/US93/05398 ~
,0~
formation of hydrogen halide gases, such as hydrogen chloride.
A wide variety of organic waste is suitable for treatment by this invention. An example of a suitable ~--5 organic waste is a hydrogen-containing carbonaceous -~
material, such as oil or a waste which includes organic compounds containing nitrogen, sulfur, oxygen, etc. It is to be understood that the organic waste can include inorganic compounds. In addition to carbon and ;
10 hydrogen, the organic waste can include other atomic ~:
constituents, such as halogens, metals, etc. Organic waste does not need to be anhydrous. However, significant amounts of water in the organic waste can cause the water to act as an oxidizing agent, thereby l~
15 interfering with the formation of an er.riched hydrogen ~
gas.~ ~For~the production of a greater yield of enriched hydrogen gas, a preferred organic waste includes a relatively high hydrogen containing carbonaaeous material, such as propane, butane, etc. For the 20 production of a greater yield of enriched carbon oxide ~`
gas, a preferred organic waste includes a low hydrogen containing carbonaceous material, such as tars, oils, ;
olefins, etc.
Organic waste is directed from organic waste - 25 source 26 through line 24 by pump 28 and is injected into molten metal 56 through organic waste tube 20. In one embodiment, the organic waste is a fluid which can ~-include organic waste components dissolved or suspended within a liquid. In another, solid particles of organic waste components are suspended in an inert gas, such as argon.
.
.
W093/2s277 PCT/US93/0~3~X ~
Organic waste directed into molten metal 56 is ~
converted to carbon, hydrogen and its other atomic ~``
constituents. The atomic hydrogen is then formed into ;
hydrogen gas i~ the absence of an oxidizing aqent and 5 the molten metal is concurrently carbonized. The term, "carbonize," as used herein, means the addition of atomic carbon to molten metal to increase the overall quantity of carbon contained in the molten metal without any substantial losses of carbon from thè -~
10 molten metal due to oxidation by a separately added oxidizing agent. It is understood,~ of course, that the organic waste may contain one or more oxidizing agents l~`
but these are not considered separately added oxidizing J
agents.
15~ ~ Hydrogen gas migrates through molten metal 56, by diff~usion, bubbling or other means. At least a portion of the hydrogen migrates to a portion of molten metal 56 proximate to off-gas outlet 18 to form an enriched hydrogen gas stream. An enriched hydrogen gas stream, 20 as that term is used herein, means a gas stream wherein ~
the;~mola~r fraction of hydrogen contained in the gas ``
stream,~based upon the total hydrogen and carbon oxide in the~gas stream, is greater than that generally l-produced in a typical process disclosed by Bach/Nagel in U.S. Patents 4,574,714 and 4,602,574 for the simultaneous, combined decomposition and ox1dation of an organic waste. ~he molar fraction of hydrogen is "
the ratio of the moles of hydrogen ~ontained in a gas `
stream to the sum of the moles of hydrogen and moles of 30 carbon oxide gases contained in the gas stream.
:
-.
: :-.:
, ~
WO 93/25277 PCr/US93/05398 2 ~3 6 ~J r The concentration of dissolved carbon in ~ .
carbonized molten metal 36 is preferably limited to an amount below the saturation point for.carbon at the temperature of molten metal 36. Thus,-;for iron, the ~-~
5 concentration of atomic carbon preferably is limited to a concentration of less than about five percent, by weight, at 1,800C. Where molten metal 36 i9 cobalt, l`
the saturation point of carbon is in the range of between about three percent at 1,400C and about 4.3 -10 percent, by weight, at 1,800C. Similarly for '.
manganese, the saturation point of carbon is~in the ~-~
range of between about eight percent at 1,400C and ~-`
about 8.5 percent, by weight, at 1,800C. For chromium ~.-the saturation point of carbon is in the range of ..
15 botween about eleven percent at 1,800C and about ..
fifteen percent, by weight, at 2,000C.
If carbon contained in the molten metal becomes insoluble because the molten metal is saturated with ~
carbon, the insoluble portion of the carbon may become -: 20 entrained in the enriched hydrogen gas stream and ~-~ : thereby be removed from the molten metal through off- ~.
: gas outlet 18. If this happens,. suitable apparatus known in the art can be used to separate the entrained ~:
carbon dust from the hydrogen gas stream. Examples of 25 suitable apparatus include a cyclone separator or .:~
baghouse~filter.
After the desired amount of an enriched hydrogen gas stream has been generated from the molten metal, a suitable separate oxidizing agent is directed from ` ~.
oxidizing agent source 38 through line 36 and is injected through oxidizing agent tube 32 into molten `
213607'1 metal 56. In one embodiment, the separate oxidizing `
agent is directed into molten metal 56 when the carbon, which is dissolved in the molten metal, approaches saturation in the molten metal. The separate oxidizing agent is directed into the molten metal separately from the organic waste. Examples of suitable oxidizing }~
agents include oxygen, air, iron oxide, etc., with the i-preferred oxidizing agent being oxygen gas.
Introduction of a separate oxidizing agent into - 10 the carbonized molten metal results in the generation of an enriched carbon oxide gas stream as carbon in the metal is oxidized to decarbonize the metal. An enriched carbon oxide gas stream, as that term is used -`~
herein, means a gas stream wherein the molar fraction of carbon oxide gas contained in the gas stream based upon the total hydrogen and carbon oxide in the gas streams,~ is greater than that generally produced in a typi~cal process disclosed by Bach/Nagel in U~.S. Patents ; 4,574,714 and 4,602,574 for the simultaneous, combined l~
decomposition and oxidation of an organic waste. The molar fraction of carbon oxide gas is the ratio of the moles~of carbon oxide;~gas contained in a gas stream to the~sum of the moles of hydrogen and moles o~f carbon oxide~gase~s~¢ontained in the gas stream.
25 ~ The~separate introduction of the oxidiz~ing agent `~
from the organic waste~into the molten metal, as that term is used herein, means an injection of oxidizing agent separate chronologically from the organic waste in order to allow the formation of a distinct hydrogen gas stream and a distinct carbon oxide gas stream to be produced. '`
'''`~' .
~V093/252'7 ~3 ~n~l~ PCT/US93/05398 Molten metal 56 has a temperature sufficient to cause the organic waste injected into molten metal 56 to be converted to carbon, hydrogen and other atomic constituents and to cause hydrogen in molten metal 56 5 to form hydrogen gas and to carbonize the molten metal. ^
Oxidizing agent, which oxidizes carbon contained in the -molten metal, is directed into molten bath after the enriched hydrogen gas is removed and forms a carbon oxide gas, thereby forming an enriched carbon oxide gas stream.
The carbon oxide gas composition ratio of carbon -monoxide to carbon dioxide can be adjusted by a number of techniques. One relates to the selection of the -metal or metals. For example, iron tends to produce carbon monoxide whereas molten nickel or manganese tends to produce an increased amount of carbon dioxide.
U.S. Patent 5,177,304, issued to Nagel (January 5, 1993), discloses a method and system for increasing the formation of carbon dioxide from carbonaceous material in a molten bath of immiscible metals. The~teachings of this patent are hereby incorporated by reference.
As taught therein, an increased amount of carbon dioxide can be produced from a molten metal bath which has two immiscible molten metals wherein the first has `
a free energy of oxidation greater than that for oxidation for atomic carbon to carbon monoxide and thè
second has a free energy of oxidation greater than that for oxidation of carbon monoxide to form carbon dioxide.
The invention described herein is not limited to the above-described embodiments. For exam~le, an '~
W O 93/25277 PCT/US93/05398 ~-~
~1~607'1 .,~.
alternative embodiment can include introducing the organic waste into the molten metal without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste, 5 whereby the molten metal is carbonized and an enriched -~
hydrogen gas stream is formed. The carbonized metal can then be solidified. At a later time, the carbonized metal can be melted, and a separate oxidizing agent can then be added into the carbonized `
10 metal to oxidize carbon contained in the carbonized ~ is molten metal to thereby form an enriched carbon oxide i`~
gas stream. ?, In yet another embodiment, molten metal can be li;
carbonized to generate an enriched hydrogen gas stream ;~-in one portion of a reactor and decarbonized with addition of a separate oxidizing agent to generate an enriched carbon oxide gas stream in another portion of the same vessel. The vessel can have a wide variety`of shapes and need not be configured as illustrated in the Figures~herein.
Illustration I
An organic waste containing an organic~compound having hydrogen and carbon, such as~ butane, is fed into a system, as shown in Figure 1. The metal is iron at a `~
25 temperature of about 1800C. The organic waste is ij decomposed to its atomic constituents, inc}uding carbon -and hydrogen in the molten metal. Hydrogen gas is generated and removed from reactor through the off-gas i~
outlet as an enriched hydrogen gas stream. The molten metal is simultaneously carbonized.
' ~ ~i . ',' .'`
W O 93/25277 PC~r/US93/05398 ,' .
~,i3601 4 ''~
After the hydrogen gas is removed, an oxidizing --agent, oxygen gas, is then added to the carbonized molten metal in the system. The reaction of carbon with the oxidizing agent occurs preferentially to the oxidation of the iron in the molten metal, because, as can be seen in Figure 2, the free energy of oxidation of carbon (Curve 1) is lower than that of the iron (Curve 2) at the temperature of the molten metal. ~-Carbon preferentially forms carbon monoxide to iron oxide or carbon dioxide because the free energy of oxidation to carbon dioxide (Curve 3) is greater than the free- energy of oxidation of iron (Curve 2) which is greater than the free energy of oxidation for carbon to form carbon monoxide (Curve }). Oxygen gas is added until carbon is removed from the molten metal. The carbon monoxide is separated from molten metal through the;off-gas outlet which can then be directed to a i~`
carbon oxide collection tank, not shown, or vented to the atmosphere.
Illustration II
In a reactor configuration similar to Illustration I, organic waste containing an organic compound having hydrogen~and carbon, such as butane, is fed into the molten metal-of the reactor. However, the molten metal `~
is nickel at a temperature of about 1800C. The organic waste forms the atomic constituents of carbon and hydrogen in the molten metal causing separation of hydrogen from carbon by the decomposition of hydrogen to form hydrogen gas. The hydrogen gas is removed from ~"
~ .
~ .
W093/25277 PCT/~S93~05398 ~136074 , reactor through the off-gas outlet in an enriched hydrogen gas stream. The molten metal is carbonized.
After the hydrogen gas is removed, oxidizing agent, oxygen gas, is then added to the carbonized molten metal. The reaction of carbon with the oxidizing agent occurs preferentially to the oxidation of the nickel in the molten metal, because, as can be ~;
seen in Figure 2, the free energy of oxidation of carbon ~Curve 1) is lower than that of the nickel (Curve 4) at the temperature of molten metal. Carbon forms a mixture of carbon monoxide and carbon dioxide ;
because the free energies of oxidation to form carbon dioxide (Curve 3) and to form carbon monoxide (Curve 1) are less than the free energy of oxidation of nickel.
Oxygen gas is added until carbon is essentially consumed in the carbonized molten metal. The carbon -~
oxide gases are separated from the molten metal through the off-gas outlet which can then be directed to a carbon oxide collection tank, not shown, or vented to 20 the atmosphere. ;
:
removed from the vessel. Thereafter, a separate oxidizing agent is added into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to generate an enriched carbon monoxide and carbon dioxide gas stream having a significantly increased ratio of carbon dioxide/carbon monoxide ;--compared to that produced in molten iron under the same conditions and decarbonizing the molten metal. The ~
enriched carbon oxide gas stream is substantially `
removed from the vessel.
This invention has the advantage of treating -organic waste to form an enriched stream of hydrogen gas and a separate enriched stream of carbon oxide gas, such as carbon monoxide or carbon dioxide or both.
Enriched hydrogen and/or carbon oxide gas streams are often desired. For example, an enriched stream of -~
hydrogen gas is particularly useful in the synthesis of ~-`
ammonia or oxoalcohol and in hydrogenation or desulfurization processes. Hydrogen is also an excellent "clean" or "greenhouse gas free" fuel.
, Brief Descri~tion of the Drawinqs ;~
Figure 1 is a schematic representation of a system ;~
for sequentially forming enriched hydrogen and enriched carbon oxide gas streams from an organic waste in `~
25 molten metal by a method according to this invention. ``
Figure 2 is a plot of the free energies at varying -temperatures for the oxidation of nickel, iron and carbon.
W093/2s277 PCT/US93/05398 ,~.
601 ~ ~
Detailed Description of the Invention ~ , The features and other details of the method of the invention will now be more particularly described s with reference to the accompanying drawings and pointed 5 out in the claims. It will be understood that the particular embodiments of the invention are shown by way of illustration and not as limitations of the invention. The principle features of this invention can be employed in various embodiments without 10 departing from the scope of the invention.
The present invention generally relates to a method for treating organic waste in molten metal to separately form enriched hydrogen and carbon oxide gas streams. This invention is an improvement of the Bach/Nagel method disclosed in U.S. Patents 4,574,714 and 4,602,S74, the teachings of which are incorporated by reference.
One embodiment of the invention is illustrated in Figure 1. Therein, system 10 includes reactor 12.
Examples of suitable reactors include appropriately modified steelmaking vessels known in the art as K-BOP, Q-BOP, argon-oxygen decarbonization furnaces (AOD), BOF, etc. Reactor 12 includes upper portion 14 and lower portion 16. Off-gas outlet 18 extends from upper portion 14 and is suitable for conducting an off-gas composition out of reactor 12.
Organic waste inlet tube 20 includes organic material inlet 22 and extends from lower portion 16 of reactor 12. Line 24 extends between organic waste source 26 and organic waste inlet tube 20. Pump 28 is disposed in line 24 for directing organic waste from W093/2s277 PCT/US93/05398 213607~
, . .
organic waste source 26 through organic waste inlet .
tube 20 and into molten metal contained in reactor 12. `
Tuyere 30 is disposed at lower portion 16 of .
reactor 12. Tuyere 30 includes oxidizing agent tube 32 for injection of a separate oxidizing agent at oxidizing agent inlet 34. Line 36 extends between oxidizing agent tube 32 and oxidizing agent source 38.
Outer tube 40 of tuyere 30 is disposed concentrically about oxidizing agent tube 32 at oxidizing agent inlet :
34. Line 42 extends between outer tube 40 and shroud .
gas source 44 for conducting a suitable shroud gas from shroud gas source 44 through the ConcentFic opening -~
. between outer tube 40 and oxidizing agent tube 32 to .
oxidizing agent inlet 34. -~t is to be understood, however, that more than ~`
one organic waste tube or more than one oxidizing agent `~.
tube, or combinations thereof, can be disposed at the :~
lower portion of reactor 12 for introduction of organic ;`-.
waste and an oxidizing agent into reactor 12. Suitable organic waste can also, optionally, be introduced into reactor 12 through port 46 and/or conducted:from organic waste source 26 through line 47 to reactor 12. . ' Other means, such as an injection lance (not shown), t : can also be employed to introduce organic waste into molten metal in carbonization reactor 12.
Bottom tapping:spout 48 extends from lawer portion -16 of reactor 12 and is suitable for removal of molten ~.
metal from reactor 12.
Induction coil 50 is disposed at lower portion 16 - 30 for heating molten metal 56 in reactor 12. It is to be ~``
understood that, alternatively, reactor 12 can be ;-`.
W093/25277 PCT/US93/OS398 ~
2!L360~
.
heated by other suitable means, such as by oxy~uel burners, electric arcs, etc. -Trunions 52 are disposed at reàctor 12 for manipulation of reactor 12. Seal 54 is disposed 5 between off-gas outlet 18 and port 46 and is suitable --for allowing partial rotation of reactor 12 about trunions 52 without breaking seal 54. --Molten metal 56 is disposed within reactor 12. In one embodiment, molten metal 56 comprises a` metal having a free energy of oxidation, at operating conditions of system 10, which is greater than the free energy for conversion of atomic carbon to carbon -monoxide. Examples of suitable metals include iron, chromium and manganese. Molten metal 56 can include more than one metal. For example, molten metal 56 can include a solution of miscible metals, such as iron and chromium.
Suitable metals are those with melting points within the operating conditions of the system. It is preferred, for example, to run system 10 in a temperature range of from about 1300C to about 1700C.
-~ guitable metals must also have a carbon solubility sufficient to allow significant amounts of hydrogen to -be generated as organic waste is decomposed and the ;
25 molten metal becomes carbonized. Thus, metals with a ~
carbon solubility of greater than about 0.5 percent, by `
weight, are preferred, and those with a carbon solubility of greater than about two percent, by weight, are particularly preferred. In the cases where -more than one metal is employed, at least one of the : , `
W093/25277 PCT/US93/05398 ~-~ .
213607 ~
. .
. -metals should have the aforementioned carbon ~ -solubility.
In many cases, it is also preferred to have the viscosity of the molten metal in reactor 12 less than about ten centipoise at the operating conditions of reactor 12. -~
Molten metal 56 is formed by at least partially filling reactor 12 with a suitable metal. The metal is ~
then heated to a suitable temperature by activation of `
10 induction coil 52 or by other suitable means, not ;~
shown. Suitable operating conditions of system 10 include a temperature sufficient to at least partially `
convert organic waste by decomposition to hydrogen and i carbon. Generally, a temperature in the range of `
~etween about 1,300 and about 1,700C is suitable.
Optionally, molten metal 56 can have vitreous or slag layer 62. Vitreous layer 62, which is disposed on molten metal 56, is substantially immiscible with `
molten metal 56. Vitreous layer 62 can have a lower thermal conductivity than that of molten metal 56.
Radiant heat loss from molten metal 56 can thereby be reduced to significantly below the radiant heat loss -from molten bath where no vitreous layer is present.
Typically, a vitreous layer 62 includes at least 25 one metaI oxide having a free energy of oxidation, at `~
the operating conditions of system 10, which is less than that for the oxidation of atomic carbon to carbon monoxide, such as calcium oxide (CaO). Vitreous layer 62 can contain a suitable compound for scrubbing `-halogens, such as chlorine or fluorine, to prevent Wos3t2s277 PCT/US93/05398 ~
,0~
formation of hydrogen halide gases, such as hydrogen chloride.
A wide variety of organic waste is suitable for treatment by this invention. An example of a suitable ~--5 organic waste is a hydrogen-containing carbonaceous -~
material, such as oil or a waste which includes organic compounds containing nitrogen, sulfur, oxygen, etc. It is to be understood that the organic waste can include inorganic compounds. In addition to carbon and ;
10 hydrogen, the organic waste can include other atomic ~:
constituents, such as halogens, metals, etc. Organic waste does not need to be anhydrous. However, significant amounts of water in the organic waste can cause the water to act as an oxidizing agent, thereby l~
15 interfering with the formation of an er.riched hydrogen ~
gas.~ ~For~the production of a greater yield of enriched hydrogen gas, a preferred organic waste includes a relatively high hydrogen containing carbonaaeous material, such as propane, butane, etc. For the 20 production of a greater yield of enriched carbon oxide ~`
gas, a preferred organic waste includes a low hydrogen containing carbonaceous material, such as tars, oils, ;
olefins, etc.
Organic waste is directed from organic waste - 25 source 26 through line 24 by pump 28 and is injected into molten metal 56 through organic waste tube 20. In one embodiment, the organic waste is a fluid which can ~-include organic waste components dissolved or suspended within a liquid. In another, solid particles of organic waste components are suspended in an inert gas, such as argon.
.
.
W093/2s277 PCT/US93/0~3~X ~
Organic waste directed into molten metal 56 is ~
converted to carbon, hydrogen and its other atomic ~``
constituents. The atomic hydrogen is then formed into ;
hydrogen gas i~ the absence of an oxidizing aqent and 5 the molten metal is concurrently carbonized. The term, "carbonize," as used herein, means the addition of atomic carbon to molten metal to increase the overall quantity of carbon contained in the molten metal without any substantial losses of carbon from thè -~
10 molten metal due to oxidation by a separately added oxidizing agent. It is understood,~ of course, that the organic waste may contain one or more oxidizing agents l~`
but these are not considered separately added oxidizing J
agents.
15~ ~ Hydrogen gas migrates through molten metal 56, by diff~usion, bubbling or other means. At least a portion of the hydrogen migrates to a portion of molten metal 56 proximate to off-gas outlet 18 to form an enriched hydrogen gas stream. An enriched hydrogen gas stream, 20 as that term is used herein, means a gas stream wherein ~
the;~mola~r fraction of hydrogen contained in the gas ``
stream,~based upon the total hydrogen and carbon oxide in the~gas stream, is greater than that generally l-produced in a typical process disclosed by Bach/Nagel in U.S. Patents 4,574,714 and 4,602,574 for the simultaneous, combined decomposition and ox1dation of an organic waste. ~he molar fraction of hydrogen is "
the ratio of the moles of hydrogen ~ontained in a gas `
stream to the sum of the moles of hydrogen and moles of 30 carbon oxide gases contained in the gas stream.
:
-.
: :-.:
, ~
WO 93/25277 PCr/US93/05398 2 ~3 6 ~J r The concentration of dissolved carbon in ~ .
carbonized molten metal 36 is preferably limited to an amount below the saturation point for.carbon at the temperature of molten metal 36. Thus,-;for iron, the ~-~
5 concentration of atomic carbon preferably is limited to a concentration of less than about five percent, by weight, at 1,800C. Where molten metal 36 i9 cobalt, l`
the saturation point of carbon is in the range of between about three percent at 1,400C and about 4.3 -10 percent, by weight, at 1,800C. Similarly for '.
manganese, the saturation point of carbon is~in the ~-~
range of between about eight percent at 1,400C and ~-`
about 8.5 percent, by weight, at 1,800C. For chromium ~.-the saturation point of carbon is in the range of ..
15 botween about eleven percent at 1,800C and about ..
fifteen percent, by weight, at 2,000C.
If carbon contained in the molten metal becomes insoluble because the molten metal is saturated with ~
carbon, the insoluble portion of the carbon may become -: 20 entrained in the enriched hydrogen gas stream and ~-~ : thereby be removed from the molten metal through off- ~.
: gas outlet 18. If this happens,. suitable apparatus known in the art can be used to separate the entrained ~:
carbon dust from the hydrogen gas stream. Examples of 25 suitable apparatus include a cyclone separator or .:~
baghouse~filter.
After the desired amount of an enriched hydrogen gas stream has been generated from the molten metal, a suitable separate oxidizing agent is directed from ` ~.
oxidizing agent source 38 through line 36 and is injected through oxidizing agent tube 32 into molten `
213607'1 metal 56. In one embodiment, the separate oxidizing `
agent is directed into molten metal 56 when the carbon, which is dissolved in the molten metal, approaches saturation in the molten metal. The separate oxidizing agent is directed into the molten metal separately from the organic waste. Examples of suitable oxidizing }~
agents include oxygen, air, iron oxide, etc., with the i-preferred oxidizing agent being oxygen gas.
Introduction of a separate oxidizing agent into - 10 the carbonized molten metal results in the generation of an enriched carbon oxide gas stream as carbon in the metal is oxidized to decarbonize the metal. An enriched carbon oxide gas stream, as that term is used -`~
herein, means a gas stream wherein the molar fraction of carbon oxide gas contained in the gas stream based upon the total hydrogen and carbon oxide in the gas streams,~ is greater than that generally produced in a typi~cal process disclosed by Bach/Nagel in U~.S. Patents ; 4,574,714 and 4,602,574 for the simultaneous, combined l~
decomposition and oxidation of an organic waste. The molar fraction of carbon oxide gas is the ratio of the moles~of carbon oxide;~gas contained in a gas stream to the~sum of the moles of hydrogen and moles o~f carbon oxide~gase~s~¢ontained in the gas stream.
25 ~ The~separate introduction of the oxidiz~ing agent `~
from the organic waste~into the molten metal, as that term is used herein, means an injection of oxidizing agent separate chronologically from the organic waste in order to allow the formation of a distinct hydrogen gas stream and a distinct carbon oxide gas stream to be produced. '`
'''`~' .
~V093/252'7 ~3 ~n~l~ PCT/US93/05398 Molten metal 56 has a temperature sufficient to cause the organic waste injected into molten metal 56 to be converted to carbon, hydrogen and other atomic constituents and to cause hydrogen in molten metal 56 5 to form hydrogen gas and to carbonize the molten metal. ^
Oxidizing agent, which oxidizes carbon contained in the -molten metal, is directed into molten bath after the enriched hydrogen gas is removed and forms a carbon oxide gas, thereby forming an enriched carbon oxide gas stream.
The carbon oxide gas composition ratio of carbon -monoxide to carbon dioxide can be adjusted by a number of techniques. One relates to the selection of the -metal or metals. For example, iron tends to produce carbon monoxide whereas molten nickel or manganese tends to produce an increased amount of carbon dioxide.
U.S. Patent 5,177,304, issued to Nagel (January 5, 1993), discloses a method and system for increasing the formation of carbon dioxide from carbonaceous material in a molten bath of immiscible metals. The~teachings of this patent are hereby incorporated by reference.
As taught therein, an increased amount of carbon dioxide can be produced from a molten metal bath which has two immiscible molten metals wherein the first has `
a free energy of oxidation greater than that for oxidation for atomic carbon to carbon monoxide and thè
second has a free energy of oxidation greater than that for oxidation of carbon monoxide to form carbon dioxide.
The invention described herein is not limited to the above-described embodiments. For exam~le, an '~
W O 93/25277 PCT/US93/05398 ~-~
~1~607'1 .,~.
alternative embodiment can include introducing the organic waste into the molten metal without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste, 5 whereby the molten metal is carbonized and an enriched -~
hydrogen gas stream is formed. The carbonized metal can then be solidified. At a later time, the carbonized metal can be melted, and a separate oxidizing agent can then be added into the carbonized `
10 metal to oxidize carbon contained in the carbonized ~ is molten metal to thereby form an enriched carbon oxide i`~
gas stream. ?, In yet another embodiment, molten metal can be li;
carbonized to generate an enriched hydrogen gas stream ;~-in one portion of a reactor and decarbonized with addition of a separate oxidizing agent to generate an enriched carbon oxide gas stream in another portion of the same vessel. The vessel can have a wide variety`of shapes and need not be configured as illustrated in the Figures~herein.
Illustration I
An organic waste containing an organic~compound having hydrogen and carbon, such as~ butane, is fed into a system, as shown in Figure 1. The metal is iron at a `~
25 temperature of about 1800C. The organic waste is ij decomposed to its atomic constituents, inc}uding carbon -and hydrogen in the molten metal. Hydrogen gas is generated and removed from reactor through the off-gas i~
outlet as an enriched hydrogen gas stream. The molten metal is simultaneously carbonized.
' ~ ~i . ',' .'`
W O 93/25277 PC~r/US93/05398 ,' .
~,i3601 4 ''~
After the hydrogen gas is removed, an oxidizing --agent, oxygen gas, is then added to the carbonized molten metal in the system. The reaction of carbon with the oxidizing agent occurs preferentially to the oxidation of the iron in the molten metal, because, as can be seen in Figure 2, the free energy of oxidation of carbon (Curve 1) is lower than that of the iron (Curve 2) at the temperature of the molten metal. ~-Carbon preferentially forms carbon monoxide to iron oxide or carbon dioxide because the free energy of oxidation to carbon dioxide (Curve 3) is greater than the free- energy of oxidation of iron (Curve 2) which is greater than the free energy of oxidation for carbon to form carbon monoxide (Curve }). Oxygen gas is added until carbon is removed from the molten metal. The carbon monoxide is separated from molten metal through the;off-gas outlet which can then be directed to a i~`
carbon oxide collection tank, not shown, or vented to the atmosphere.
Illustration II
In a reactor configuration similar to Illustration I, organic waste containing an organic compound having hydrogen~and carbon, such as butane, is fed into the molten metal-of the reactor. However, the molten metal `~
is nickel at a temperature of about 1800C. The organic waste forms the atomic constituents of carbon and hydrogen in the molten metal causing separation of hydrogen from carbon by the decomposition of hydrogen to form hydrogen gas. The hydrogen gas is removed from ~"
~ .
~ .
W093/25277 PCT/~S93~05398 ~136074 , reactor through the off-gas outlet in an enriched hydrogen gas stream. The molten metal is carbonized.
After the hydrogen gas is removed, oxidizing agent, oxygen gas, is then added to the carbonized molten metal. The reaction of carbon with the oxidizing agent occurs preferentially to the oxidation of the nickel in the molten metal, because, as can be ~;
seen in Figure 2, the free energy of oxidation of carbon ~Curve 1) is lower than that of the nickel (Curve 4) at the temperature of molten metal. Carbon forms a mixture of carbon monoxide and carbon dioxide ;
because the free energies of oxidation to form carbon dioxide (Curve 3) and to form carbon monoxide (Curve 1) are less than the free energy of oxidation of nickel.
Oxygen gas is added until carbon is essentially consumed in the carbonized molten metal. The carbon -~
oxide gases are separated from the molten metal through the off-gas outlet which can then be directed to a carbon oxide collection tank, not shown, or vented to 20 the atmosphere. ;
:
Claims (13)
1. A method of treating an organic waste containing hydrogen and carbon in molten metal contained in a vessel to sequentially form enriched hydrogen and carbon oxide gas streams comprising the steps of:
a) introducing the organic waste into molten metal, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to form an enriched hydrogen gas stream and carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate oxidizing agent into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to form an enriched carbon oxide gas stream and to decarbonize the molten metal;
and d) removing substantially all of the formed enriched carbon oxide gas stream from the vessel.
a) introducing the organic waste into molten metal, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to form an enriched hydrogen gas stream and carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate oxidizing agent into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to form an enriched carbon oxide gas stream and to decarbonize the molten metal;
and d) removing substantially all of the formed enriched carbon oxide gas stream from the vessel.
2. A method of Claim 1 wherein the enriched carbon oxide gas stream comprises carbon monoxide.
3. A method of Claim 2 wherein the molten metal comprises iron.
4. A method of Claim 3 wherein the separate oxidizing agent comprises oxygen gas.
5. A method of Claim 1 wherein the enriched carbon oxide gas comprises a mixture of carbon monoxide and carbon dioxide gases.
6. A method of Claim 5 wherein the molten metal is selected to provide a significantly increased molar ratio of carbon dioxide/carbon monoxide compared to that produced in molten iron.
7. A method of Claim 5 wherein the molten metal comprises manganese.
8. A method of Claim 5 wherein the molten metal comprises two immiscible metals having a first immiscible metal having a free energy of oxidation, at the conditions of the molten metal, greater than that of oxidation of atomic carbon to form carbon monoxide and a second immiscible metal having a free energy of oxidation, at the conditions of the molten metal, greater than that of oxidation of carbon monoxide to form carbon dioxide.
9. A method of Claim 8 wherein said molten metal comprises an immiscible mixture of iron and copper.
10. A method of treating an organic waste containing hydrogen and carbon in molten metal contained in a vessel to sequentially form enriched hydrogen and carbon oxide gas streams, said carbon oxide gas having a significantly increased molar ratio of carbon dioxide/carbon oxide compared to that produced in molten iron under the same conditions, comprising the steps of:
a) introducing the organic waste into molten metal which comprises two immiscible metals wherein, at the operating conditions, the first immiscible metal has a free energy of oxidation greater than that for oxidation of carbon to carbon monoxide and the second immiscible metal having a free energy of oxidation greater than that for oxidation of carbon monoxide to carbon dioxide, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate oxidizing agent into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to generate an enriched carbon oxide gas stream having a significantly increased ratio of carbon dioxide/carbon monoxide compared to that produced in molten iron under the same conditions; and d) removing substantially all of the formed enriched carbon oxide gas stream from the vessel.
a) introducing the organic waste into molten metal which comprises two immiscible metals wherein, at the operating conditions, the first immiscible metal has a free energy of oxidation greater than that for oxidation of carbon to carbon monoxide and the second immiscible metal having a free energy of oxidation greater than that for oxidation of carbon monoxide to carbon dioxide, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate oxidizing agent into the carbonized molten metal to oxidize carbon contained in the carbonized molten metal to generate an enriched carbon oxide gas stream having a significantly increased ratio of carbon dioxide/carbon monoxide compared to that produced in molten iron under the same conditions; and d) removing substantially all of the formed enriched carbon oxide gas stream from the vessel.
11. A method of treating an organic waste containing hydrogen and carbon to sequentially form enriched hydrogen and carbon monoxide gas streams, comprising the steps of:
a) introducing the organic waste into molten iron contained within a vessel, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate stream of oxygen gas into the carbonized molten iron to oxidize the carbon contained in the carbonized molten iron to thereby form an enriched carbon monoxide gas stream and to decarbonize the molten metal iron; and d) removing substantially all of the formed enriched carbon monoxide gas stream from the vessel.
a) introducing the organic waste into molten iron contained within a vessel, without the addition of a separate oxidizing agent and under conditions sufficient to decompose the organic waste and to generate an enriched hydrogen gas stream and to carbonize the molten metal;
b) removing substantially all of the formed enriched hydrogen gas stream from the vessel;
c) thereafter adding a separate stream of oxygen gas into the carbonized molten iron to oxidize the carbon contained in the carbonized molten iron to thereby form an enriched carbon monoxide gas stream and to decarbonize the molten metal iron; and d) removing substantially all of the formed enriched carbon monoxide gas stream from the vessel.
12. In a method for treating an organic waste containing hydrogen and carbon by introducing the organic waste into molten metal contained in a vessel under conditions sufficient to decompose the organic waste and including the addition of an oxidizing agent to the molten metal to form hydrogen and carbon oxide gases:
the improvement of generating enriched hydrogen and carbon oxide gas streams by introducing the organic waste into molten metal without the addition of said oxidizing agent thereby carbonizing the molten metal and forming a separate enriched hydrogen gas stream and after substantially removing the enriched hydrogen gas stream, separately:
introducing said oxidizing agent into the carbonized molten metal to decarbonize said molten metal, thereby generating a separate enriched carbon oxide gas stream.
the improvement of generating enriched hydrogen and carbon oxide gas streams by introducing the organic waste into molten metal without the addition of said oxidizing agent thereby carbonizing the molten metal and forming a separate enriched hydrogen gas stream and after substantially removing the enriched hydrogen gas stream, separately:
introducing said oxidizing agent into the carbonized molten metal to decarbonize said molten metal, thereby generating a separate enriched carbon oxide gas stream.
13. The improvement of Claim 12 wherein the molten metal is carbonized and decarbonized in the same reactor vessel to generate enriched hydrogen and carbon oxide gas streams.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89535892A | 1992-06-08 | 1992-06-08 | |
| US07/895,358 | 1992-06-08 |
Publications (1)
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|---|---|
| CA2136074A1 true CA2136074A1 (en) | 1993-12-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136074A Abandoned CA2136074A1 (en) | 1992-06-08 | 1993-06-08 | Method for treating organic waste |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0644789B1 (en) |
| JP (1) | JPH07507591A (en) |
| AT (1) | ATE148636T1 (en) |
| AU (1) | AU667118B2 (en) |
| BR (1) | BR9306669A (en) |
| CA (1) | CA2136074A1 (en) |
| DE (1) | DE69308020T2 (en) |
| DK (1) | DK0644789T3 (en) |
| ES (1) | ES2097521T3 (en) |
| GR (1) | GR3022911T3 (en) |
| MD (1) | MD960181A (en) |
| RU (1) | RU2118192C1 (en) |
| WO (1) | WO1993025277A1 (en) |
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|---|---|---|---|---|
| US6254652B1 (en) * | 1995-04-13 | 2001-07-03 | Marathon Ashland Petroleum Llc | At least three-step molten metal decomposition process cycle |
| US6274045B1 (en) | 1995-05-19 | 2001-08-14 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| US6270679B1 (en) | 1995-05-19 | 2001-08-07 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| US6254782B1 (en) | 1995-05-19 | 2001-07-03 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| US5753125A (en) * | 1995-05-19 | 1998-05-19 | Kreisler; Lawrence | Method for recovering and separating metals from waste streams |
| US6797195B1 (en) | 1995-05-19 | 2004-09-28 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| EP0954511A1 (en) * | 1996-11-22 | 1999-11-10 | Ashland Inc. | Molten metal reactor and process |
| WO2010130404A1 (en) * | 2009-05-14 | 2010-11-18 | SCHLÜTER, Hartwig | Method and system for performing chemical processes |
| DE102013112205A1 (en) * | 2012-11-06 | 2014-05-08 | Technische Universität Dortmund | Apparatus, used to produce hydrogen by thermal decomposition of e.g. methane, comprises pyrolysis reactor having reaction chamber present in form of capillary, and unit for adjusting flow rate of high-temperature heat transfer medium |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2843997A1 (en) * | 1978-10-09 | 1980-04-10 | Kloeckner Humboldt Deutz Ag | gasification of fuels in molten metal bath - contg. sulphur- and carbon-binding metals |
| DE3203435A1 (en) * | 1982-02-02 | 1983-08-11 | Klöckner-Werke AG, 4100 Duisburg | METHOD FOR GAS PRODUCTION AND METAL EXTRACTION IN A MELT BATH REACTOR, IN PARTICULAR IRON BATH REACTOR |
| DE3434004C2 (en) * | 1984-09-15 | 1987-03-26 | Dornier System Gmbh, 7990 Friedrichshafen | Process and device for waste gasification |
| US4574714A (en) * | 1984-11-08 | 1986-03-11 | United States Steel Corporation | Destruction of toxic chemicals |
| DE3614048A1 (en) * | 1986-04-25 | 1987-11-05 | Kloeckner Humboldt Deutz Ag | METHOD AND DEVICE FOR GASIFYING LOW-QUALITY FUELS IN A FLUID METAL MELTING BATH |
| ATE184633T1 (en) * | 1990-06-21 | 1999-10-15 | Ashland Inc | IMPROVED METAL SNOW BATH DECOMPOSITION APPARATUS AND METHOD |
| US5177304A (en) * | 1990-07-24 | 1993-01-05 | Molten Metal Technology, Inc. | Method and system for forming carbon dioxide from carbon-containing materials in a molten bath of immiscible metals |
| BR9206400A (en) * | 1991-07-29 | 1994-12-27 | Molten Metal Tech Inc | Method and system for converting a feed product to a dissolved atomic constituent |
| DK0571577T3 (en) * | 1991-12-06 | 1999-03-08 | Tech Resources Pty Ltd | Waste treatment |
-
1993
- 1993-06-08 DK DK93915232.8T patent/DK0644789T3/en active
- 1993-06-08 MD MD96-0181A patent/MD960181A/en unknown
- 1993-06-08 ES ES93915232T patent/ES2097521T3/en not_active Expired - Lifetime
- 1993-06-08 AU AU45292/93A patent/AU667118B2/en not_active Ceased
- 1993-06-08 BR BR9306669A patent/BR9306669A/en not_active Application Discontinuation
- 1993-06-08 JP JP6501635A patent/JPH07507591A/en active Pending
- 1993-06-08 AT AT93915232T patent/ATE148636T1/en not_active IP Right Cessation
- 1993-06-08 RU RU94046361A patent/RU2118192C1/en active
- 1993-06-08 WO PCT/US1993/005398 patent/WO1993025277A1/en active IP Right Grant
- 1993-06-08 CA CA002136074A patent/CA2136074A1/en not_active Abandoned
- 1993-06-08 EP EP93915232A patent/EP0644789B1/en not_active Expired - Lifetime
- 1993-06-08 DE DE69308020T patent/DE69308020T2/en not_active Expired - Fee Related
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1997
- 1997-03-26 GR GR970400596T patent/GR3022911T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| RU2118192C1 (en) | 1998-08-27 |
| DK0644789T3 (en) | 1997-08-18 |
| ES2097521T3 (en) | 1997-04-01 |
| EP0644789A1 (en) | 1995-03-29 |
| AU667118B2 (en) | 1996-03-07 |
| ATE148636T1 (en) | 1997-02-15 |
| JPH07507591A (en) | 1995-08-24 |
| MD960181A (en) | 1998-07-31 |
| EP0644789B1 (en) | 1997-02-05 |
| AU4529293A (en) | 1994-01-04 |
| DE69308020T2 (en) | 1997-05-22 |
| WO1993025277A1 (en) | 1993-12-23 |
| GR3022911T3 (en) | 1997-06-30 |
| RU94046361A (en) | 1997-04-27 |
| DE69308020D1 (en) | 1997-03-20 |
| BR9306669A (en) | 1998-12-08 |
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