CROSS REFERENCE TO RELATED APPLICATIONS This application is related to Attorney's Docket 6391QPC, filed November 25, 1996, and Attorney's Docket 6391PPC, filed November 25, 1996.

BACKGROUND OF THE INVENTION 1. FTELD OF THE INVENTION This invention relates to a process of conversion of hydrocarbons via gasification into two higl1 pressure gas streams: a hydrogen-rich stream and a carbon- monoxide-rich stream. More specifically, this invention relates to the use of a two- zone predominantly molten iron or molten iron alloy system in conjunction with the above gasification conversion.

II. DTSCUSSION OF THE PRIOR ART Two-zone molten iron gasifiers are disclosed by: U.S. Patent 1,803,221(1931) to Tyrer describes hydrogen-nch gas production by feeding methane or a methane-steam mixtul-e into one molten iron zone below the surface of the metal, thereby assuring complete reaction of the gaseous feed. The

carbon which dissolves in the molten iron in the first zone is burned out of the molten iron in the second zone with an oxygen containing gas. Additional oxygen containing gas may be added to the combustion products leaving the second zone to completely oxidize to carbon dioxide any carbon monoxide remaining.

The disadvantages of the process described in this patent include: The feedstocks are limited to hydrocarbon gases such as methane and do not include lower value hydrocarbon liquids or solids.

Operating pressure is nominally atnospheric pressure which is less economical to operate than equipment producing hydrogen at elevated pressures; two atmospheres and above.

The importance of controlling the carbon level in the molten iron is not considered and thus production of only lower purity hydrogen-rich gas is possible. If a minimum carbon level of at least 0.3% is not maintained, excess iron oxide will form in the molten iron during oxidation and will be converted to carbon monoxide and dilute the llydrogen-rich gas when hydrocarbon feeds are introduced to the hydrogen-rich gas producing first zone.

U.S. Patents 4,187,672 (1980) and 4,244,180 (1981) to Rasor describe a hydrocarbon gasification process in which solid hydrocarbons such as coal are introduced on the surface of one molten iron bath zone in which high temperature cracking of the hydrocarbons into lighter molecular weight materials takes place with

residual carbon being dissolved in the molten iron. The cracked hydrocarboll products are removed via outlets in the shaft tllrough which the feed hydrocarbon solids enter the molten iron. The molten iron containing the carbon is transterred to the second molten iron zone in which an oxygen containing gas is introduced to convert the carbon into carbon monoxide and raise the temperature of the iron for transfer back to the carbonization section. The carbon monoxide is further oxidized above the molten iron bath and the heat recovered via a boiler or similar system. Sulfur, if present in the feed, is removed via slag formation on top of the molten iron. The disadvantages of the process described in this patent include: The feedstocks are limited to solid hydrocarbons such as coal and do not include lower value hydrocarbon liquids or gases.

Since the solid hydrocarbon feeds are introduced above the surface of the molten iron, cracking of the feeds occurs such that a very impure hydrogen gas stream is produced because of the presence of cracked hydrocarbon gases.

Since the product gas from the oxidation zone is further oxidized for energy recovery in, for example, a steam boiler, no attempt is made to produce a carbon monoxide-nch gas.

Sulfur removal from the solid feed via reaction with and removal of slag from the equipment is complicated and expensive.

Operating pressure is nominally atmospheric pressure, which is less economical to operate that equipment producing hydrogen at elevated pressures; two atmospheres and above.

The importance of controlling the carbon level above 0.3% in tloe molten iron is not considered and thus production of only lower purity hydo-ogen-nch gas is possible.

U.S. Patent 5,435,814 (1995) to Miller and Malone (Ashland) describes the general concept of a two-zone molten iron system process operating at high pressures, up to 1 00 atmospheres, witll solid and liquid feed introduction below the surface of the molten iron and production of a hydrogen-ricl? and carbon monoxide rich gas streams. The disadvantages of the process described in this patent include: There is no method described for handling the feedstock sulfide.

The importance of controlling the carbon level in the molten iron is not considered and thus production of only lower purity hydrogen-riclo gas may be possible. The process is restricted to a particular method of circulating molten iron.

In summary, all of the above patents operate at atmosplleric pressure and do not control carbon at a minimum of 0.3% in molten iron. Furthermore, the Rasor patents do not inject feed below the surface of the molten iron and are restricted to solids feeds. Furthermore, all the patents ignore sulfur in the feed or use slag to remove it.

One-zone molten metal gasifiers are disclosed by:

U.S. Patents 4,496,369 (1985) to Torneman and 4,511,372 (1985) to Axelsson in whicll coal or other liquid hydrocarbons are injected advantageously below the surface of the molten iron along with oxygen and water vapor to forum a mixed hydrogen and carbon monoxide gas. Iron oxides are also added to the molten iron to act as a coolant for the melt. The primary objective of tloe invention is to produce gasified hydrocarbons and it is disclosed that production can be increased by operating at lligll pressures. The thigh pressures are not only economic because of the reduced size of equipment but it is also disclosed that high pressure decreases the degree of refractory wear in the reactor and the amount of dust carry-over in the gas from the reactor. In addition, it is disclosed that a higher sulfur level in tloe molten bath will also reduce the amount of dust catry-over from the reactor. The process disclosed cites the advantage of maintaining the carbon content of the bath below 0.8% carbon to reduce the amount of dust carry-over from the reactor.

The primary disadvantage of the process described in this patent include the lack of separate molten iron zones for gasification and thereby does not pennit production of individual loydrogen-riclo and carbon monoxide-rich gas streams.

U.S. Patents 4,574,714 and 4,602,574 (1986) to Bach and Nagel itl which solid or liquid toxic and/or lower value hydrocarbons are injected advantageously below floe surface of the molten iron alloy, along with oxygen specifically to destroy tloe toxic compounds. With appropriate feeds a mixed hydrogen and carbon monoxide gas can

be fonned and C l chemistry may be utilized to advantage at times to produce useful products. It is further disclosed that maintaining a carbon level of 0.5-6% carbon, preferably 2-3% carbon in the molten metal is desired to prevent refractory degradation and facilitate reaction kinetics by providing a high concentration gradient for toxics destruction. Sulfur, when present in the feed, is removed via absorption in the slag. The disadvantages of the process described in this patent include: The feedstocks are introduced to the molten iron single zone system for destruction as hazardous materials and not to produce loydrogen-rich or carbon monoxide-rich gases and thereby misses the advantages of feeding non-hazardous feedstocks.

Sulfur removal from the solid feed via reaction with and removal of slag from the equipment is complicated and expensive.

Operating pressure is nominally atmospheric, which is less economical to operate than equipment producing gases at elevated pressures; two atmospheres and above. Also, rotating gasification vessels on trunnions for slag removal makes operating at higher pressures impractical.

The importance of controlling the carbon level in the molten iron at more than 0.3% is not considered and thus production of only lower purity hydrogen-rich gas is possible.

The primary disadvantage of the process described in this patent include the lack of separate molten iron zones for gasification and thereby does not permit production of individual hydrogen-rich and carbon monoxide-rich gas streams.

The following foreign patents also disclose processes related to that of this application.

U.K. Patent 1,187,782 (1970) to Nixon discloses a reactor in which a hydrocarbon is introduced to one zone resulting in the production of a hydrogen-rich gas and oxygen is introduced into a second zone where the carbon which was dissolved ill the first zone is burned with oxygen to give the exothermic heat to maintain the appropriate temperature in the first zone. It is noted that the two zone system as described has an advantage over hydrogen production in a single zone system which is operated in "blocked out" operations equivalent to that of a two zone system. It is further disclosed that sulfur present in the iron may be removed, purifying to some extent the iron. The disadvantages of the process described in this patent include: Since no attempt is made to produce a carbon monoxide-rich gas in the oxidation zone, only a hydrogen-rich gas stream is produced.

Operating pressure is nominally atmospheric pressure, which is less economical to operate tloan equipment producing hydrogen at elevated pressures; two atmospheres and above.

The importance of controlling the carbon level above 0.3% in the molten iron is not considered and thus production of only lower purity hydrogen-rich gas is possible.

One embodiment of U.K. Patent 1,437,750 (1976) to Agarwal and Ahner describes producing a combustible gas containing a ratio of hydrogen to carbon monoxide of between 2:5 to 10:1 using a two-zone molten iron reactor with a coal feed to the top of one zone. Although the gases are produced in separate zones after furtller conversion witch, for example, the water gas shift reaction, they are combined so the product from the system is a single combustible gas. Carbon concentrations in the molten iron are between 1 and 3% in the first zone and between 3 and 5% in the second zone. The disadvantages of the process described in this patent include: The feedstocks are limited to solid hydrocarbons such as coal and do not include lower value hydrocarbon liquids or gases.

Since the solid hydrocarbon feeds are introduced above the surface of the molten iron, cracking of the feeds occurs such that a very impure hydrogen gas stream is produced because of the presence of cracked hydrocarbon gases.

Since the product gas from tloe oxidation zone is combined with the gas from the first zone, no attempt is made to produce a carbon monoxide-rich gas.

No disclosure is made concerning sulfur removal from the solid feed via reaction in the molten metal zones.

Operating pressure is nominally atmospheric pressure, which is less economical to operate that equipment producing hydrogen at elevated pressures; two atmospheres and above.

U.K. Patent 2,189,504 (1987) to Herforth describes a two-zone molten iron reactor in which low grade solids fuels are gasified in one zone and hill1 grade solid fuels are gasified in the second zone. This pennits tulle low grade solid fuels and waste materials to be constuned and produce a low quality off-gas where as tulle gasification of high grade fuels in the second zone pennits production of a high quality off-gas untnixed with the low quality off-gas while still pennitting destruction of the low grade fuels or waste materials. The sulfur is removed in the slag fonned in the reactors. The disadvantages of the process described in this patent include: The feedstocks are limited to solid hydrocarbons such as coal and do not include lower value hydrocarbon liquids or gases.

Since the solid hydrocarbon feeds are introduced above the surface of the molten iron, cracking of the feeds occurs such that a very impure hydrogen gas stream is produced because of the presence of cracked hydrocarbon gases.

No attempts are made to produce either a loydrogen-riclo or carbon monoxide- rich off-gas.

Sulfur removal from the solid feed via reaction with and removal of slag from the equipment is complicated and expensive.

Operating pressure is nominally atmospheric pressure, which is less economical to operate that equipment producing hydrogen at elevated pressures; two atmospheres and above.

French Patent 2,186,524 (1974) to Vayssiere describes a two-zone molten iron system with a hydrogen-riclo gas generated from hydrocarbons injected beneath the surface of the molten iron in one zone and either a carbon monoxide-rich gas or mixture of hydrogen and carbon monoxide gas generated by injecting oxygen or oxygen and hydrocarbon into the second zone. The disadvantages of tloe process described in this patent include: There is no provision for removal of the sulfur in the feed.

Operating pressure is atmospheric pressure, which is less economical to operate that equipment producing gases at elevated pressures; two atmospheres and above.

The importance of controlling the carbon level above 0.3% in the molten iron is not considered.

In sumtnary, while such systems referenced above may provide reasonable results, none of them effect the production of a separate hydrogen-rich stream and a separate carbon monoxide-rich stream at elevated pressures by feeding hydrocarbons below the surface of the molten iron and with controlled carbon contents of the molten metal above 0.3%. Furthennore, these systems either have no provision for handling feed sulfur or use a complicated and costly slag technique for sulfur removal. Sulfur

capture in the slag requires slagging materials to be added to the molten metal zones and a more complicated means of regularly drawing off the sulfur containing slag.

When sulfur is captured in slag the slag must then be disposed of, typically in uneconomic and environmentally unsound landfills Thus, our survey of prior practices indicates that the prior art has not combined the use of two zone molten iron gasifiers for separate hydrogen-riclo and carbon monoxide-ricl1 gas production, feed introduction below the molten iron surface, higll pressure operation and carbon content control of the molten iron in the manner we have.

SUMMARY OF THE INVENTION Broadly, this invention involves a process for producing in separate streams a hydrogen-licll gas and a carbon monoxide-rich gas from two molten metal zones and necessary ancillary equipment. Molten metal components are intended to include any molten material layer within a particular zone; e.g., molten metals, such as iron and its alloys, which are always present and slag components, if present, that would fonn a second molten layer with such molten metals. The molten metal employed in this invention is preferably molten iron but may be copper, zinc, especially chromium, manganese, or nickel, or other meltable metal in which carbon is somewhat soluble and which is at least 50% molten iron by weight.

In the first molten metal zone, a hydrocarbon feed in the fonn of a relatively dry gas or liquid or solid or solid-liquid slurry or atomized solid or liquid is fed beneath the molten metal surface and a loydrogen-riclo gas is produced. By relatively dry is meant below 1% by weight of water. By introducing the feed below the surface of the molten metal substantially complete chemical reactions and conversions to hydrogen and carbon ofthe feed can be acllieved. The carbon in tloe hydrocarbon feed dissolves in the molten metal.

In the second molten metal zone, into which molten metal from the first molten metal zone flows, an oxygen bearing stream is introduced to convert the carbon dissolved in the molten metal from the first zone into a carbon monoxide-rich gas stream which exits from above tlle molten metal bath in a gas stream separate from the hydrogen-riclo gas stream from the first molten metal zone. Molten metal from which the carbon has been gasified by oxygen in the second zone is returned to the first molten metal zone.

Both molten metal zones are operated at elevated pressures, above two ahnospheres, to reduce the size of the equipment need to produce and further treat, if necessary, the hydrogen-rich and carbon-monoxide rich gases. In addition, as disclosed is U.S. Patent 4,511,372 incorporated by reference, operation at thigh pressures reduces dust carry over and wear on refractory walls of the vessel.

Furthennore, the capital and operating costs of compression, of these gases to

pressures at which tloey are utilized commercially are eliminated or substantially reduced.

Fur-thennore, in this process tloe amount of carbon in the molten iron to which tloe hydrocarbon feed is introduced is carefully controlled to above 0.3% to minimize formation of loiglo levels of FeO, ferrous oxide, which could include a separate FeO phase. Higlo levels of FeO will react witlo the carbon in the hydrocarbon feed and produce thigh levels of carbon monoxide, thereby contaminating the loydrogen-riclo stream. If a separate please of FeO is present it will attack the refractory of the vessels holding the molten iron. The amotmt of carbon in tloe molten iron should not normally exceed an upper limit as detennined by its solubility in molten iron.

This invention also includes having floe hydrogen-rido and carbon monoxide-rich gases flowing from the molten metal zones thorough separate product gas lines to pass tllrough successive downstream coolers, scrubbers or other gaseous impurity removal devices, and knock-out drums to cool the gases and to remove any solids and any condensed liquids from the gas streams. The gases may further be fed to proven scrubbers which remove hydrogen sulfide and other volatile sulfur compounds produced in the molten metal zones and emit a substantially sulfior-free and carbon oxide-free hydrogen-rich product gas and a substantially sulfior-free carbon monoxide- rich product gas.

Suitable feeds for the process include carbonaceous reactant feedstocks selected from the group consisting of: light gaseous hydrocarbons such as methane, ethane, propane, butane, natural gas, and refinery gas; heavier liquid loydrocarbons such as naphta, kerosene, asphalt, hydrocarbon residua produced by distillation or other treatment of crude oil, fusel oil, cycle oil, slurry oil, gas oil, heavy crude oil, pitch, coal tars, coal distillates, natural tar, crude bottoms, and used crankcase oil; solid hydrocarbon such as coal, rubber, tar sand, oil shale, and hydrocarbon polymers; and mixtures of the foregoing.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a drawing of the basic process of this invention.

Figure 2 is a drawing of a variation of the process of this invention incorporating scrubbing systems to remove hydrogen sulfide and other volatile sulfur compounds from tlle hydrogen-rich and carbon monoxide-rich gases made in the process.

Figure 3 is a drawing of a variation of tulle process of this invention incorporating the use of feed and product valving systems to/from two molten metal reactors to duplicate the effect of creating two molten metal zones separately by feed and product control systems instead of transferring the molten metal between two zones of a single reactor.

DETAILED DESCRIPTION OF THE INVENTION Figure 1 illustrates the invention in a simplified diagram of an apparatus for carrying out tloe basic process. Molten iron 2 is contained in the vessel 1. The molten iron in vessel l is maintained at a temperatures between 1150" and 1750°C (2102"-3182"F) to keep it substantially liquid. Partition 3 divides the vessel into two zones 4 and 5. A hydrocarbon feed in tloe fonn of a relatively dry liquid or solid or solid-liquid slurry or atomized solid or liquid in a gas is fed through tuyere pipe 6 or lance pipe 7 beneath tloe molten metal surface of zone 4 in which the hydrocarbon is converted to a hydrogen-rich gas which escapes from the surface of the molten metal and carbon which dissolves in the molten metal. The hydrogen-ricll gas exits zone 4 <BR> <BR> <BR> <BR> <BR> via pipe I 10 and enters a cooling system 11 where it is cooled to temperatures suitable for its introduction into commercial loydrogen-riclo gas consuming processes. Suitable equipment for controlling the pressure above 2 atmospheres is provided before tloe hydrogen-rich gas is sent to a consuiooioog process via pipe 13. Molten iron containing dissolved carbon from zone 4 is transferred to zone 5 and oxygen is introduced beneath the molten metal surface in zone 5 througll tuyere pipe 8 or lance pipe 9. The carbon in the molten iron in zone 5 is converted to a carbon monoxide-riclo gas in zone 5 and exits the vessel via pipe 14 and enters a cooling system 15 where it is cooled to temperatures suitable for its introduction into commercial carbon monoxide-rich gas consuming processes. Suitable equipment for controlling the pressure above 2

atmospheres is provided before the carbon-monoxide-ricl1 gas is sent to a consuming process via pipe 17.

The following additional features characterize the process illustrated in Figure 1: Suitable feeds for the process introduced via tuyere pipe 6 or lance pipe 7 include carbonaceous reactant feedstocks selected from the group consisting of: light gaseous hydrocarbons such as methane, ethane, propane, butane, natural gas, and refinery gas; heavier liquid hydrocarbons such as naphta, kerosene, asphalt, hydrocarbon residua produced by distillation or other treatment of crude oil, fuel oil, cycle oil, slurry oil, gas oil, heavy crude oil, pitch, coal tars, coal distillates, natural tar, crude bottoms, and used crankcase oil; solid loydrocarbon such as coal, rubber, tar sand, oil shale, and hydrocarbon polymers; and mixtures of the foregoing.

If the feeds introduced via tuyere pipe 6 or lance pipe 7 include sulfur, the sulfur will be removed from the system via its capture in a slag floating on the molten iron in zones 4 and 5. Or the sulfur will remain as hydrogen sulfide or other volatile sulfur compounds in the hydrogen-rich and carbon monoxide-rich gas streams and go to the gas consuming processes via pipes 13 and 17.

Any dust and fume generated as part of the process in zones 4 and 5 will be removed from the hydrogen-rich and carbon monoxide-rich gas streams via conventional means such as bag filters which are part of the gas cooling systems 11

and 15.

The amount of carbon in tloe molten iron which is returned to zone 4 from zone 5 to wloiclo the hydrocarbon feed is introduced is carefully controlled to above 0.3% at all times to 1minimize formation of a separate phase of FeO, ferrous oxide. If present in substantial amounts, the FeO will react with the carbon in the hydrocarbon feed entering via tuyere pipe 6 or lance pipe 7 and produce carbon monoxide thereby diluting the hydrogen-rich stream exiting zone 4 via pipe 10. In addition, FeO in a separate phase will attack tloe refractory lining of vessels holding the molten iron. The amount of carbon in the molten iron which passes from zone 4 to zone 5 should not nonnally exceed an upper limit as set by the solubility of carbon in molten iron.

The molten metal employed in this invention as bath 2 is preferably and predominantly molten iron but may be copper, zinc, especially chromium, manganese, or nickel, or other meltable metal in which carbon is somewhat soluble but is at all times at least 50 wt.% molten iron.

Figure 2 is drawing of a variation of the basic process. In addition to incorporating all the elements of Figure 1 including the description above, in this variation the sulfur in the feed is allowed to build up to equilibrium levels in the molten metal and slag in zones 4 and 5. At equilibrium, the sulfur compounds in the slag and metals will be converted to hydrogen sulfide and other volatile sulfide compounds in zones 4 and 5 and exit in the hydrogen-rich and carbon monoxide-rich

gases via lines ] 0 and 14. After cooling in systems 11 and 15 the sulfur compounds are removed from tloe gases by conventional means such as amine scrubbing, caustic scrubbing, or other suitable sulfur compound removing devices, etc. in sulfur removal systems 1 2 and 16 before the now essentially sulfur-free gases enter the gas consuming processes via pipes ] 3 and 17. The advantage of this mode of operation is a reduced production of slag and reduced dust formation as shown in tloe prior art, U.S. Patent 4,511,372 which is hereby incorporated by reference.

Figure 3 is a drawing of another variation of the process incorporation all of the applicable descriptions of Figures 1 and 2 and incorporating the use of feed and product valving systems to/from two molten metal reactors to duplicate the effect of creating two molten metal zones separated by feed and product control systems instead of transferring the molten metal between two zones of a single reactor.

In this variation, as shown in Figure 3, the process comprises two (or more) identical systems performing functions comparable to the systems in Figures 1 and 2 and including: vessels 11 and 21 holding molten iron in baths 12 and 22; feed tuyere pipes 16 and 26 and alternative feed lance pipes 17 and 27 for introducing loydrocarbon feeds below the surface ofthe molten iron 12 and 22; feed tuyere pipes 18 and 28 and alternative feed lance pipes 19 and 29 for introducing oxygen below the surface of the molten iron ] 2 and 22; vessel exit pipes 10 and 20; gas cooling systems 13 and 23; and product gas pipes 60 and 50.

This system duplicates the two-zone reactor system of Figures 1 and 2 by creating the equivalent of two zones with the use of suitable valves and control systems on the feeds to vessels 1] and 21 and the product gases exiting the cooling systems 13 and 23 via pipes 60 and 50. Thus, tloe control systems are operated such that while hydrogen-rich gas is being made in vessel 11 and carbon monoxide-rich gas is being made in vessel 21. After an appropriate length of time operating in this mode the feed and product control systems switches the feeds and products and hydrogen rich gas is made in vessel 21 and carbon monoxide-rich gas is made in vessel ] 1. The hydrocarbon feed system is described as follows: hydrocarbons are conducted to the system in pipe 40 which divides into pipes 41 and 44; pipe 41 leads to valve 42 and pipe 43 which is connected to tuyere pipe 26 or lance pipe 27 in vessel 21; pipe 44 leads to valve 45 and pipe 46 which is connected to tuyere pipe 16 or lance pipe 17 in vessel 11. Tlie oxygen feed system is described as follows: oxygen is conducted to the system in pipe 30 which divides into pipes 31 and 34; pipe 31 leads to valve 32 and pipe 343 which is connected to tuyere pipe 28 or lance pipe 29 in vessel 21; pipe 34 leads to valve 35 and pipe 36 which is connected to tuyere pipe 18 or lance pipe 19 in vessel 11. The determination of whether hydrocarbons or oxygen are fed to either vessel 11 or 21 is detenooined by whether valves 32, 35, 42 and 45 are open or shut; these settings, in turn, being established by the control system.

The product gas systems from vessel Ii is described as follows: product gases exit vessel 11 via pipe 10, pass tlorouglo cooling system ] 3 and enter pipe 60; the gases may tloeio go via pipe 61 through valve 62 into pipe 63 and pipe 54 comlecting with tloe commercial processes using hydrogen-rich gas; or the gases may go via pipe 65 tllrougll valve 66 into pipe 67 and pipe 58 connecting with tloe commercial processes using carbon monoxide-rich gas. The product gas systems from vessel 21 is described as follows: product gases exit vessel 2 i via pipe 20, pass through cooling system 23 and enter pipe 50; the gases may tben go via pipe 51 tlorouglo valve 52 into pipe 53 and pipe 54 collecting with the colwnercial processes using hydrogen-rich gas; or the gases may go via pipe 55 through valve 56 into pipe 57 and pipe 58 connecting with the commercial processes using carbon monoxide-rich gas. The routing of each gas is detennined by whether valves 62, 66, 52 and 56 are open or shut; these settings, in turn, being established by the control system.

As an example of the operation of the system in Figure 3, if hydrogen-riclo gas were being produced in vessel 11 and carbon monoxide-rich gas were being produced in vessel 21, tloe following valves would be open; 45, 32, 62, 56, and closed; 42, 35, 66, 52. These valve settings would be reversed when hydrogen-rich gas were being produced in vessel 21 and carbon monoxide-rich gas were being produced in vessel 11. The system for Figure 3 loas been described in simple tenns for the general concept. A more detailed description of tile operation is given in USSN 08/425,938,

filed April 19, 1995, (attomey's docket 6501AUS) which is incorporated by preference.

This application also describes the use of three molten metal vessels, instead of two, with a similar valving and control system to pennit continuous gasification operations when one reactor must be out of service for repairs, etc. This feature is also included in the present disclosure by reference.

Another variation of the process is to use an oxygen enriched gas as the source of oxygen through tuyere pipe 8 or lance pipe 9 (Figures I and 2) for gasifying the dissolved carbon in the molten metal in zone 5.

Another variation of tloe process is to use liquid feedstocks prior to their introduction to the system via tuyere pipe 6 or lance pipe 7 as a scrubbing medium in the cooling sections 11 and 15 for dust and fume removal from the hydrogen-rich and carbon moaoxide-ricil product gases exiting vessel 1 through pipes 10 and 14 (Figures land 2).

Another variation of tloe process is to use a quantity of hydrogen-rich gas from pipe 13 (Figures 1 and 2) or elsewhere in the system to atomize liquid hydrocarbon feeds as they are introduced to zone 4 via tuyere pipe 6 or lance pipe 7.

Another variation of the process is to use a quantity of carbon monoxide-rich gas pipe 17 (Figures 1 and 2) or elsewhere in the system to cool tuyere pipe 8 or lance pipe 9 introducing tloe oxygen to the molten metal in zone 5.

Another variation of the process is to use a quantity of water vapor or steam to cool tuyere pipe 8 or lance pipe 9 introducing the oxygen to the molten metal in zone 5 and to moderate tlle temperature in zone 5.

Another variation of the process is to use a quantity of carbon dioxide gas to cool tuyere pipe 8 or lance pipe 9 introducing the oxygen to tlle molten metal in zone 5 and to moderate the temperature in zone 5.

Another variation of the process is to use a quantity of methane gas to cool tuyere pipe 6 or lance pipe 7 introducing the feed to the molten metal in zone 4 and to moderate the temperature in zone 4.

The following explanation details the importance to this invention of controlling the amount of oxygen introduced to the carbon monoxide-rich gas generation section such that flie carbon content of the molten iron returned to the hydrogen-rich gas generation section is above a minimum value and thereby ensures that the hydrogen-rich gas contains a minimum of impurities. It also emphasizes the importance of these controls particularly when operating at the high pressures of this invention. Reference (by page number and/or figure number) are made to the data in tloe book, "The Making, Shaping and Treating of Steel", Tenth Edition, Copyright 1985 by Association of Iron and Steel Engineers.

The desired primary chemical reaction taking place in toe hydrogen-riclo gas generation section of this invention involves the gasification of a hydrocarbon feed (CHl,) CH,, n/2 H2 (hydrogen gas) + C- Fe (carbon dissolved in molten iron) (1) However, two important and undesirable secondary reactions will take place between the carbon itl the feed and any oxygen and iron oxide (FeO) which is present in the molten iron: C + O - Fe (oxygen dissolved in molten iron) = CO (carbon monoxide gas) + Fe(molten) (2) C + FeO (separate phase in molten iron) = CO (carbon monoxide gas) + Fe (molten) (3) Reactions (2) and (3) are undesirable since carbon monoxide gas is generated which dilutes the hydrogen gas produced by reaction (1) and thereby requires more extensive loydrogen-rich gas purification facilities. In addition, it is known that FeO in a separate phase will attack refractory linings of vessels holding molten iron to a greater extent than just molten iron so that the conditions for Reaction 3 to take place should be minimized or eliminated, that is, there should be no separate FeO phase present with the molten iron.

Similarly, the desired chemical reaction taking place in the carbon monoxide- rich gas generation section of the invention involves the oxidation of the carbon dissolved in the molten iron coming from the hydrogen-rich gas generation section: 2C - Fe (carbon dissolved in molten iron) + O2 = 2CO + Fe(molten) (4) Again, there are two undesirable secondary reactions which take place between the iron and the oxygen fed to this section: Fe + O2 = ° - Fe (oxygen dissolved in molten iron) (5) 2Fe + O2 = 2FeO (separate phase in molten iron) (6) Note that the chemical elements shown in the above equations are illustrative of the materials involved and the processes taking place but may not necessarily represent tloe actual molecular species which may be present. For example, experimental evidence has shown that: a) oxygen dissolved in molten iron may be present as dissolved FeO or in other iron/oxygen ratios; b) carbon dissolved in molten iron may be present as dissolved FeC or in other iron/carbon ratios.

It is an important feature of this invention that the process must be controlled based on a complete understanding of the factors which control the degree to which all the above reactions, and in particular the secondary reactions (reactions 2, 3, 5, 6) will take place. The following quantitative relationships are critical to this understanding.

When oxygen and molten iron are present, oxygen is soluble to a limited extent in molten iron; the maximum soliibility being 0.16% at 1527"C (2781°F) (page 405 in reference). Graphically, the solubility of oxygen at other temperatures is presented in Figure 13-542 while matl1ematically it is described by (page 406): log [wt.% O] = - 6320/T(°K) + 2.734 (7) If more oxygen is added to molten iron than will be soluble according to tloe above, the oxygen reacts with the iron and a separate FeO phase is formed (page 405).

Wloen oxygen and carbon and molten iron are present, the amount of oxygen in the molten iron as well as the amount of carbon in the molten iron are related according to the following reaction (page 674): CO (pressure above molten iron) = 0 + C (concentrations in molten iron)(8) and equation K = [wt.%C]x[wt.% O]/Pco (partial pressure CO, atm) (9) log K = -1168/T (OK) - 2.07 (10) The fact that the concentrations of carbon and oxygen dissolved in molten iron are proportional to and affected by the partial pressure of the carbon monoxide above the molten iron is critical to the process control and successful commercial application of this invention. This trend is illustrated by the following example.

According to Equation 7 the solubility of oxygen in molten iron at 1 4820C (27000F) is 0.136 wt.%. Thus, if more than 0.136 wt.% oxygen is present in the

molten iron, it will be present as a separate phase of FeO. According to Equation 9, the following amounts of oxygen will be present in molten iron at 1482C (27000F) wllen the molten iron contains 0.3 wt.% and 4.5 wt.% carbon at various pressures of carbon monoxide above the molten iron bath: CO Pressure psia wt.% 0 at 0.3% Carbon wt.%Oat4.5%Caibon 0.147 0.000061 0.000004 1.47 0.000613 0.000041 ]47 0.00613 000041 294.0 0.1226 0.0082 485.1 0.2023 0.0135 735.0 0.3060 0.0204 It is observed that, when the CO pressure is at 485.1 or 735.0 psia and the carbon in the molten iron is at 0.3 wt.%, the amount of oxygen is present in the molten iron is above 0.136 wt.% (floe maximum solubility of oxygen) and thus a separate FeO phase will also be present. These are conditions sunder which the carbon monoxide-rich section of the invention could be operated and would be the composition of the molten iron circulated to the hydrogen-rich gas generation section.

Wllen circulated back to the hydrogen-rich gas generation section tloe pressure of the carbon monoxide would be minimum and the dissolved oxygen and FeO would react be released as carbon monoxide into the hydrogen-rich gas by Reactions 2 and 3 above and thereby dilute the ldrogen-rich gas. In addition the refractory holding the molten iron would be subject to attack by the FeO. Although, the amount of dissolved oxygen in the molten iron cannot be controlled, the amount of FeO as a separate phase

can by controlling the amount of carbon in the molten iron in the carbon monoxide- rich gas generation section. This would be done by regulating the amount of oxygen introduced into the carbon monoxide-rich gas generation section such that the amount of carbon in the molten iron did not fall below a specific prescribed level for the given operating conditions. According to Equation 9 at 14820C (2700OF) the amount of carbon in the molten iron to Ininimize the foI7nation of a separate phase of FeO should be above 0.446 wt.% at 485.1 psia and 0.676 wt.% at 735 psia.

While using specific quantities for demonstration purposes, the above example illustrates the trends involved in the control of the operations of the invention but in no way limits the operating conditions to those shown. Other operating temperatures and pressures will determine appropriate carbon and oxygen content lisnitations for the molten iron.

What is claimed is: