WO1980002151A1

WO1980002151A1 - Process and apparatus for carbonaceous material conversion

Info

Publication number: WO1980002151A1
Application number: PCT/US1980/000332
Authority: WO
Inventors: W Mayes
Original assignee: Cosden Technology
Priority date: 1979-04-02
Filing date: 1980-04-01
Publication date: 1980-10-16
Also published as: BE882491A; ZA801909B; ES8203950A1; CA1144948A; ES497332A0; GB2065161B; NL8020136A; ES490128A0; IL59769A0; GB2065161A; JPS56500343A; PL223113A1; IT1130572B; PT71047B; IT8020937A0; DD150073A5; BR8007917A; ES8104379A1; KR830001885B1; FR2452965A1

Abstract

A process for conversion of a carbonaceous feed material (2) into gaseous products, comprising the steps of: contacting a carbonaceous feed material with a molten mass medium in the lower section of a substantially vertical, elongated reaction zone (1) to form a mixture of carbonaceous feed material and molten mass medium, whereby at least one gaseous material is present and a multi-phase mixture is formed; hydraulically transporting the multi-phase mixture substantially upwardly through the reaction zone to the upper section thereof and with a velocity sufficient to establish a gas lift effect to provide improved yields in a chemical conversion reaction producing a modified multi-phase mixture; passing the modified multi-phase mixture to a separation device (6); and separating the modified multi-phase mixture into a gaseous product(s) stream (7) and a liquid stream (9) comprising said molten mass medium; and apparatus for carrying out the process.

Description

PROCESSANDAPPARATUSFORCARBONACEOUSMATE ^_O3^^I0N

TECHNICAL FIELD

The present invention relates to conversion of carbonaceous materials in a molten mass reaction medium. More particularly, the invention relates to a process and apparatus for conversion of carbonaceous materials in a molten mass medium wherein at least a portion of the reactants is in the gaseous phase to facilitate intimate and uniform contact between the reactants and the molten mass medium, short reaction times and independent control of the ratio of molten mass flow rates to feed flow rates through the reaction zone. The invention may be used to simultaneously conduct more than one continuous chemical reaction in a common molten mass medium with continuous transfer of molten mass medium between several reaction zones in series or in parallel operation without the aid of a mechanical pump, and the reaction zones may be operated at differing pressures.

BACKGROUND ART

Over the past many years, various investigators have recorded the conversion of hydrocarbonaceous materials employing a molten mass medium for such conversions. The predominant category of molten mass used as a medium for conversion processes and/or equipment has been various molten salts. For example, some of the more recent U. S. Patents include No. 3,252,773; 3,252,774; 3,567,412; 3,619,144; 3,708,270; 3,170,737; 3,740,193; 3,758,673; 3,916,617; 3,941,681; and 4,017,271. These enumerated patents suggest the use of a molten alkali metal salt as the reaction medium in the gasification of hydrocarbon feed materials. Similarly, U. S. Patents No. 3,553,279; 3,081,256; 3,745,109; 3,582,188; 3,862,025; 3,871,992; and 3,876,527 disclose the use of a molten alkali metal salt as a reactant medium in the cracking of hydro- carbon feedstocks to produce ethylene. As a further example of the prior art, molten salts have also been suggested for use in the dehydrogenation of hydrocarbon feedstocks in U. S. Patents No. 3,270,086; 3,309,419; 3,449,458; 3,586,733; 3,637,895; and 3,697,614. As an additional example, U. S. Patents No. 3,387,941 and 3,440,164 disclose the use of alkali metal salts as a reaction medium in the desulfurization of hydrocarbon materials.

Heretofore, the reported use of a molten mass as a reaction or conversion medium has been limited to process and mechanical designs which are restricted to relatively low capacity as opposed to design systems which lend themself to commercial use. Moreover, the necessity of maintaining feed rates at low levels in the prior art molten mass methods becomes particularly disadvantageous in - those types of conversion reactions wherein yields are disadvan¬ tageous^ affected by long contact times between the molten mass and the hydrocarbon reactants. U. S. Patents No. 2,031,987; 3,852,188; 3,862,025; 3,871,992; and 3,876,527 also suggest that the hydrocarbon feed may be con¬ currently contacted with the molten mass. However, in order to achieve sufficient separation between the molten mass and the gaseous hydrocarbonaceous materials to permit product recovery, the feed rates must again be restricted to undesirably low levels, which limit processing capacities and adversely affect product yields. It has also been suggested in U. S. Patent No. 2,055,313 that the hydrocarbon feed may be used to hydraulically transport a molten mass reaction medium. However, in the method of this reference, the actual conversion of hydrocarbonaceous feed occurs by contacting the molten mass in a countercurrent flow there¬ between. Again, the capacity of the largest practical size equip¬ ment built in accordance with this teaching would be limited to the rate at which gaseous reactants could disengage from the molten mass at the interfacial level.

OMPI SUMMARY OF THE INVENTION

The present invention has as its object the provision of a process and apparatus for converting carbonaceous materials in a molten mass reaction medium which overcome the deficiencies of the prior art in that it has a high capacity, produces improved product yields, and facilitates short contact times between the carbonaceous reactants and the molten mass medium.

It is also the object of the present invention to provide a process and apparatus wherein several different reactions may be carried out in separate reaction zones at differing pressures utilizing a common molten mass reaction medium which is circulated without the aid of a pump.

The object of the invention also includes a process and apparatus in which there is an intimate and uniform contact between reactants and the molten mass, and wherein the ratio of reactants to molten mass in each reaction zone may be independently controlled. In accomplishing the foregoing and other objects, there has been provided in accordance with the present invention, a process for the conversion of carbonaceous feed materials into more valuable products which accrues substantial savings in capital investment costs and improved product yields as compared with the prior art molten mass hydrocarbon conversion methods. This process comprises contacting a carbonaceous feed material, with a molten mass medium maintained at a temperature above the melting point of the molten mass medium in a substantially vertical, elongated hydrocarbon conversion zone(s), with a substantially upward co-current flow

OMPI of feed and molten mass medium, and with a velocity sufficient to establish preferably at least a froth flow transport condition hereinafter defined through the reaction zone; and then separating the co-current flow of feed and molten mass medium into a stream of more valuable products and a stream of a molten mass medium at the upper portion of the reaction zone. A flow of lower turbulence (or flow rate) may be designed and operated, but the economic benefits would be greatly reduced. By employing a co-current froth flow of reactants and molten mass, applicant has found that flow rates as great as ten times those possible with the prior art molten mass processes may be successfully utilized. As a result of the much higher feed rates possible with the process of the instant invention, commercially significant quantities of hydro¬ carbon feed material may be efficaciously processed with a much smaller equipment size requirement than that of the prior art molten mass processes and equipment. Moreover, through the use of a co-current froth flow contacting of the molten mass and carbonaceous reactants, the present invention enables the contact time between the molten mass and carbonaceous feed (or reactants) to be adjusted to very low levels, on the order of 1 second or less, accruing thereby a significant improvement in product yield. In other words, by enabling the use of greater feed velocities, the present invention enables the use of a time-temperature profile which is more optimum for hydrocarbon conversion reactions. Broadly, the process of the present invention may be utilized in any molten mass medium hydrocarbon conversion reaction. The molten mass medium and the hydrocarbon feed must be contacted with

OMPI a co-current flow in a vertically elongated reaction zone wherein the gaseous feed and/or reactant and/or diluting gas form a hydrau¬ lic flow pattern of sufficient turbulence to represent preferably the froth or more turbulent type of hydraul c transport flow as hereinafter defined. Any suitable transport velocity above this typical value may be successfully, and in certain situations preferably, utilized in the practice of the present invention. It is advantageous to select a hydraulic flow pattern and a ratio of molten mass to gaseous feed and/or gaseous reactants and/or gaseous diluting materials for an economical balance between operating costs and intimate contact. For example, the hydraulic transport of molten mass and hydrocarbon feed and/or reactants through the reaction zone may occur such that an annular mode of hydraulic transport condition as hereinafter defined, or a mist hydraulic transport condition, or any hydraulic transport condition inter¬ mediate therebetween is produced in the reaction zone.

As used herein, the term "froth flow" transport condition refers to that hydraulic condition, or degree of turbulence, within the mixed phase reaction zone or zones which is necessary to estab- lish and maintain the circulation of molten mass reaction medium by the phenomenon known in the art as air lift or gas lift. The optimum design is achieved by a turbulence greater than the minimum. The optimum degree of turbulence for each molten mass reaction zone will need to be determined separately, but the applicant has found the most logical design in several molten medium systems to be in the "froth flow" pattern such as is described and set forth in Anderson, R.J., and Russell, T. .F., "Chemical Engineering"

BUR

OM 7 ^" December 6, 1965. Certain flow conditions characterized by those authors as "slug flow" may meet the definition of "froth flow" according to the present invention because the requisite gas lift effect is produced. It is intended that such conditions also fall within the scope of the term "froth flow" as used in this applica¬ tion and thereforewithin the scope of the present invention.

The process of the instant invention is particularly suit¬ able for use in the cracking of a high sulfur content hydrocarbon feed material into more valuable products, and is simultaneously suitable for partial oxidation of the carbonaceous product from the cracking reaction. The molten mass medium may be selected so as to readily retain essentially all of the sulfurous compounds which are liberated during the cracking and during the partial oxidation reactions, and such a molten mass medium- is readily re- generated to remove the retained sulfur therefrom without the necessity of prior costly desulfurization treatment of the feed. Moreover, a further advantage of the instant invention is that a single supply of molten mass medium may be employed to sustain a plurality of chemical reactions by recycling the molten mass medium therebetween. The hydrocarbon conversion reaction may occur in conjunction with an exothermic reaction, such as, for example, a partial oxidation reaction, whereby the heat released in the exothermic (oxidation) reaction zone is utilized to furnish the necessary heat of reaction for other reactions or conversions which are endothermic. This transfer of heat from exothermic reac¬ tion zones is facilitated by the circulation of molten mass between the respective zones, thus allowing the molten mass to carry heat in the form of sensible heat of the molten mass medium. The cir¬ culation rate required to transfer the necessary heat is dependent upon temperature differences between the respective reaction zones, and the heat capacities of the molten mass utilized. Independent of the heat transfer requirements being satisfied by the circula¬ tion of molten mass between the respective exothermic and endo- thermic reactions, recirculation of molten mass from a separation device and back to the respective lower section of a vertically elongated froth flow hydraulic transport reaction zone(s) enables the designer to control the ratio of molten mass to feed and/or reactants and/or diluting gas within each transport reaction zone.

O BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic flow diagram of a closed-cycle gasification process employing the inventive concepts of the present invention; Figure 2 is a schematic flow diagram of a continuous gasification process for a sulfur-containing carbonaceous feed material according to the invention;

Figure 3 is a schematic flow diagram of a two reaction zone system according to the invention utilizing a common molten medium;

Figure 4 is a schematic flow diagram of a system similar to that illustrated in Figure 3; and

Figure 5 is a schematic flow diagram illustrating a three reaction zone system according to the invention employing a common molten medium.

OMPI DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Applicant has found that through the use of the co-current froth flow hydraulic transport concept of the instant invention, feed velocities as great as ten times those possible with the prior art molten mass processes may be utilized through single train equipment, a range of feed rates which enables molten mass tech-^' nology to be commercially utilized for the first time in the conversion of tonnage quantity carbonaceous feed materials. Broadly, the process of the instant invention is highly suitable for use in any type of hydrocarbon conversion reaction well known to those skilled in the art, as well as in any other type of chemical reaction capable of being conducted in a molten reaction medium. By way of illustration, but not of limitation, suitable reactions which may be conducted in accordance with the instant invention include cracking, oxidation, partial oxidation, gasification, methanization, polymerization, dealkylation, desul- furization, reforming, isomerization, dehydrogenation, oxidative dehydrogenation, the catalyzed versions thereof, combinations thereof, or any of the processes described in U. S. Patents No. 3,252,773; 3,252,774; 3,449,458; 3,081,256; 3,708,270; 3,710,737: 3,745,109; 3,916,617; 4,017,271; 3,871,992; 3,862,025; 3,852,118; 2,031,987; 2,055,313; 3,387,941; 3,440,164; 3,270,086; 3,309,419; 3,587,733; 3,637,895; 3,697,614; 3,553,279; 3,567,412; 3,619,144; 3,740,193; 3,758,673; 3,941,681; 3,948,759; 2,053,211; 2,334,583; 2,354,355; 2,100,823; 2,074,529; 3,449,458; and 2,682,459. The only limit upon the particular type of reaction process and equip¬ ment to which the principle of the instant invention can be applied

OMP 7 λ , is that the particular reaction be capable of being carried out in a molten reaction medium and must have a gas reactant or gas diluent in sufficient amount to create a froth flow as herein defined in a vertically elongated reaction zone. A detailed listing of other types of organic reactions which can be conducted in molten medium is set forth in Advances in Molten Salt Chemistry, Vol. 3, Plenum Press (New York 1975), Library of Congress Catalog No. 78-131884. Each of the aforementioned types of reactions is well known to those skilled in the art, and the molten mass techniques of the instant invention are highly suitable for use therein.

The molten medium may comprise any molten material suitable for use as a reaction medium in reactions of the above-discussed type. A requirement for successful practice of the instant inven¬ tion is that the molten medium be sufficiently fluid to permit hydraulic mixing followed by separation and be stable at the reaction temperatures and pressures employed to allow the reaction to proceed. Typically, the molten medium with which the hydro¬ carbon feed is brought into contact will comprise a molten metal selected from Groups I-VIII of the Periodic Chart of the Elements or a molten metal salt which is molten within the temperature range between about 50°C and about 2500°C, and which is of suffi¬ ciently low volatility that loss of the molten medium with product gas is minimized. Preferred materials for use as the molten medium comprise alkali metal melts, mixtures of alkali metal melts molten alkal metal salts, mixtures of molten alkali metal salts, and mixtures of molten alkali metals and alkali metal salts. Suit¬ able alkali metal salts are the alkali metal carbonates, hydroxides, nitrates, sulfides, chlorides and oxides, of which the carbonates, sulfides, chlorides, and hydroxides are preferred. Use of the car¬ bonate is particularly advantageous when removal of sulfur from the product is desired, as the carbonate has the ability to react with sulfurous compounds which are liberated from the feedstock at elevated temperatures during the overall reaction.

While it is possible to employ a single alkali metal salt as the reaction medium, it is often preferred to employ a eutectic or near eutectic mixture, e.g., binary, ternary, quaternary, etc. Particularly preferred for use as the molten medium in the instant invention are mixtures of alkali metal salts, such as alkali metal carbonates, examples of which include sodium carbonate-potassium carbonate-lithium carbonate; sodium carbonate-lithium carbonate; potassium carbonate-lithium carbonate and sodium carbonate-potas- sium carbonate, as well as any other salts thereof. Mixtures of the alkali metal salts comprise ideal candidates for use as the molten medium in the instant invention since these materials tie up sulfur very readily and can be easily regenerated. When the process of the instant invention is being utilized for the gasifi- cation of carbonaceous feed materials, a single alkali metal salt may be utilized with advantage since the higher temperatures employed therein allow the use of a molten medium with a higher melting point. Particularly preferred in this regard is sodium carbonate since this material is readily available in the typical refining or petrochemical complex, and can be supplied from otherwise waste caustic. The present invention also contemplates that the molten medium may also contain an additional catalytic material admixed there¬ with in order to enhance and promote the carbonaceous materials conversion reaction. When a promoter or αatalyst material is utilized, the molten medium will usually contain from about 0 to 50% by weight of the promoter or catalyst materials, and preferably will contain about 25% by weight of the promoter or catalyst material or less.

The carbonaceous material utilized as the feed material in the instant process may comprise any carbon-containing material well known to those skilled in the art. Suitable carbonaceous feed materials include vegetable and mineral oils, other naturally occurring carbonaceous materials, asphalts, hydrocarbon residiums produced by distillation or distillation and solvent extraction of crude oil, fuel oils, cycle oil, gas oil, rubbers, heavy crude oils pitch, coal tar, coal, natural tars, hydrocarbon-containing polymers, tar sand oil, naphtha, shale oil, natural gas, refinery gas, light hydrocarbons, e.g., ethane, propane, and butane, kerosene, shredded automobile tires, automobile crank case oil drainage, etc., and mixtures or products thereof.

The carbonaceous feed material may comprise a high sulfur content carbonaceous feed material. Examples of feed materials of this type include the heavy hydrocarbon feed stocks, such as, crude oils, heavy residiums, the asphalts, hydrocarbon residiums produced by distillation or distillation and solvent extraction, crude bottoms pitch, other heavy hydrocarbon pitch-forming residua, coal, coal tar or distillates, natural tars, cycle oil, slurry oil, tar sand, and oil shale. Of particular interest are high sulfur content, low ash materials such as asphalts, cycle oil, tar sand oil, shale oil, slurry oil, and the hydrocarbon residiums and aromatic tars. The carbonaceous feed and the molten medium are contacted with a co-current flow through the reaction zone and with veloci¬ ties sufficient to establish preferably at least a "froth flow" transport condition in the reaction zone, as defined above. The exact feed rate necessary to establish this type of transport phenomenon will vary, e.g., with the particular molten medium utilized, the particular carbonaceous feed stock and the necessity to maintain contact times within certain limits, and this feed rate can be readily determined by those skilled in the art. The particular transport^'velocity actually employed can vary over wide ranges, provided that the transport conditions are sufficient to establish at a minimum the gas lift effect transport condition as above defined through the reaction zone, and in practice the velocity will frequently be greater than the minimum level which is necessary to produce this gas lift effect. For example, in those types of hydrocarbon conversion reactions such as cracking and partial oxidation or gasification, wherein the hydrocarbon conversion reaction is favored by minimal contact times, very high transport velocities will generally be employed in order to reduce the contact time to a minimum. In addition, the use of multi-phase froth flow transport eliminates the necessity for pumps in order to circulate the molten mass throughout the process equipment.

In the cracking of asphalt to produce ethyl.ene, for example, using a molten medium comprising a mixture of potassium and lithium carbonates containing approximately 1% by weight alkali metal sulfide under steady-state operating conditions, typical feed rates will include a carbonaceous feed rate corresponding to a reaction zone superficial velocity of about 10 to 100 ft/second, and preferably about 20 to 35 ft/second; and a molten mass to carbonaceous feed weight ratio of about 2 to 20, and preferably about 4 to 8 depending on heats of reaction, heat capacity of molten mass, and temperature differences between reaction zones. With reaction zone conditions in this range, contact times of from about 0.5 to 10 or more seconds are readily obtainable. Similarly, in the gasification of carbonaceous materials to produce low or medium BTU gas, using a sodium carbonate molten medium containing from about 0 to 25 percent by weight alkaline metal sulfide under steady state operating conditions, air and steam are typically fed in a ratio to control the overall heat generation such that said total heat is (1) removed in the form ^' of sensible heat of the exiting product gas, and (2) lost through the walls of the container. Temperature is therefore controllable by the adjustment of the ratio of air to steam. Typical air rate is from 3 to 7 pounds of air per pound of carbonaceous feed and typical feed rate of steam is from about 0.2 to 0.5 pounds of water vapor per pound of carbonaceous feed. The transport reactor is sized such that the gaseous and liquid mixture typically rises upwardly at a velocity which corresponds- to the superficial velo- city of from about 25 to 100, preferably 10 to 80 and typically 10 to 40 feet per second. While not essential to the reaction, an inert diluent can be employed in order to regulate or control the partial pressure of reactants in the molten medium reaction zone, and/or to assist in the gas lift of the mult -phase hydrocarbon-molten medium mixture. Diluents which may be employed include helium, carbon dioxide, nitrogen, steam, methane, and the like. In those types of carbon¬ aceous material conversion reactions in which the presence of hydrogen is necessary or desirable, such as in reforming, hydro- desulfurization, or hydrocracking, suitable quantities of hydrogen gas may also be injected into the reaction zone. The inert diluent would typically be employed in a mole ratio of from about 0.1 to 50 mols of diluent per mol of carbonaceous feed or reactant, and more perferably from about 0.1 to 1.

The present invention is particularly suitable for use in the cracking and partial oxidation or gasification of heavy carbon¬ aceous feedstocks of high sulfur content, the conversion of which ^• has heretofore not been as economically beneficial by conventional methods as is desired due to the product states achievable and/or the excessive coking in the reaction zones, and the necessity for extensive desulfurization treatments to reduce the high sulfur content thereof. The present process and equipment are suited for those high sulfur content hydrocarbon conversion reactions which are favored by minimal contact times, such as, for example, the cracking of heavy carbonaceous feedstocks to ethylene and other products. Accordingly, the instant process will be described with reference to preferred embodiments involving the cracking and partial oxidation or gasification of heavy hydrocarbon feedstocks to produce ethylene and other products and a low or medium BTU gas, respectively, although it is to be emphasized that the present invention provides a broad reaction technique which is suitable for use in any type of chemical conversion reaction capable of being conducted in a molten reaction medium.

Generally, in the cracking of asphalts and other heavy hydrocarbon feedstocks to produce ethylene, the hydrocarbon feed will be contacted with a mixture of alkali metal carbonates or a mixture of alkali metal carbonates and alkali metal sulfides at a temperature of from about 600 to 850°C, and a pressure of from about 0.5 to 10 atmospheres, preferably approximately 1 atmosphere absolute. The feed rates of the hydrocarbon feedstock and the molten medium are adjusted such that a- froth flow transport condi¬ tion is established in the reaction zone, with a contact time of a maximum of about 25 seconds. Preferably, the feed rates will be adjusted to provide a contact time of less than about 5 seconds and most preferably, of about 1 second or less, since ethylene production is favored by a minimum contact time-high temperature reaction profile. Optionally, a suitable diluent gas, such as steam or hydrogen, may be admixed with the multi-phase mixture of molten salt and hydrocarbon feed, with a steam and/or hydrogen to reactants mole ratio in the range of from about 0.1 to 1.0 and preferably with a steam and/or hydrogen to reactants mole ratio of about 0.3. ; In the partial oxidation or gasification of heavy hydro¬ carbonaceous feedstocks or the carbonaceous product of for example cracking to produce a low or medium BTU gas comprising predominantly carbon monoxide and hydrogen, the hydrocarbon feed will typically be contacted with an alkal metal carbonate molten medium, or a mixture of alkali metal carbonates and sulfides, at a temperature of from about 800 to 1200°C, preferably at a temperature of approximately 1000°C, and with a pressure of from about 1 to 20 atmospheres absolute. A suitable molten medium may comprise sodium carbonate or an admixture of sodium carbonate and sulfide since at the temperatures employed, the sodium metal salt is molten and very fluid. The use of sodium metal salt as the molten medium is also desirable since this material is lower in cost than most other media and also has a very high affinity for retaining sulfur oxides. The gasification reaction proceeds almost instantaneously, and the contact time will generally be less than about 10 seconds, preferably less than about 5 seconds, and most preferably less than about 2.0 seconds. The specific oxygen feed rates will vary depend¬ ing upon whether air, pure oxygen, or some other oxygen-containing ^' gas is utilized. The ratio in oxygen-containing gas to carbonaceous feed material is controlled so that the production of carbon monoxide and hydrogen from the feedstock is preferred. In order to control the temperature by the amount of water gas reaction, steam will usually be injected into the reaction zone, the specific amount necessary increasing with increasing temperature. Where the partial oxidation is operated in conjunction with an endothermic reaction to supply the heat therefor, it may be necessary to control the heat evolution by a means such as injecting steam to promote a water-gas reaction. Where it is desirable to obtain complete oxidation of the feedstock, the same reaction conditions will usually be employed, with the exception that the amount of oxygen or oxygen-containing gas addition will be increased sufficiently to provide complete oxidation. If the oxidization is employed in conjunction with a cracking reaction to supply heat, and the carbonaceous material formed in the cracking reaction is not sufficient to sustain the heat requirement, additional feed (same as or different from that supplied to cracking reaction zone) may be added directly into the oxidation zone.

In a further embodiment of the instant invention, a hydrocarbon conversion reaction in accordance with the present invention is combined with a second reaction or reactions in order to take advantage of the heat transfer capacity of the molten reaction medium to sustain a plurality of different reactions. For example, in the cracking of heavy carbonaceous feeds, it is desirable to conduct the cracking reaction in conjunction with an exothermic coke oxidation or partial oxidation reaction whereby the coke contained in the molten medium as a result of the cracking reaction may be utilized as an energy source to maintain the temperature in the endother ic cracking reaction zone in a closed cycle type operation. Additionally, a sulfur removal reaction may be conducted in conjunction with the cracking reaction and/or the carbon oxidation reaction to convert the sulfide contained in the molten medium as a result of the cracking and/or oxidation reaction into valuable hydrogen sulfide- gas. A significant ad- vantage of the use of molten mass technology in the conversion of carbonaceous material is thus that it readily lends itself to use in multiple reaction processing operations.

OMPI Referring now to the drawings, Figure 1 illustrates a continuous gasification process according to the instant invention in its simplest form. In this Figure, a single reaction zone is employed, wherein the molten mass is circulated in a closed cycle system. Carbonaceous feed is introduced through line 2 into the lower section of a mixed phase gasification reaction zone 1. An oxygen containing gas, and steam if desired, and optionally a di¬ luting gas, enter the lower section of said zone through line 3. Molten mass medium enters the lower section of said mixed phase gasification zone 1 through line (or conduit) 4. The feed may be admixed with oxygen containing gas and/or steam, if any and/or diluting gas, if any, prior to entering the lower section of said zone. Upon mixing of feed, steam, oxygen containing gas, and di¬ luting gas with hot molten medium in said lower section of said zone, the mixed phase mixture flows in a co-current, turbulent flow pattern to the upper section of said vertical, elongated ^" gasification zone 1, and during this transport the chemical reac¬ tions proceed. From the upper section of said gasification zone, the mixed phase consisting of gaseous products and a liquid con- taining molten mass and any unreacted liquid or solid reactants flow through conduit 5 to a separation device, herein shown as a cyclone 6. In the cyclone 6, the gaseous products exit from the upper section of said cyclone through line 7 for use or separation elsewhere. The liquid portion of the mixed phase fluid entering cyclone 6 is directed to the lower section of said cyclone by the action of the cyclone and exits said lower section through line 9. The accumulation of liquid in the system causes an interfacial

_ OM

,^< WIP level 8, which may be maintained in the lower section of cyclone 6 or in line 9. As shown in Figure 1, line 9 becomes line 4 which directs the return of molten medium back to the lower section of the said gasification zone 1 to complete the closed cycle of molten medium in this reaction system. The circulation rate of molten medium and unreacted^' liquid or solid reactants may be adjusted in operation by increasing or decreasing the inventory of molten medium so as to raise or lower the interfacial level 8 within line 9 and/or cyclone 6 (a higher level resulting in an increased flow rate for the molten medium). With some types of feedstock there will be an accumulation of heavy metals in the form of elemental metal, or oxides, or compounds thereof, and/or ash which can be controlled by continuously or intermittently withdrawing molten medium from the system and replacing same by makeup. Reference is now made to Figure 2, which is a schematic flow diagram of a continuous gasification process for a sulfur- containing carbonaceous feed materials. In this figure, molten medium flows in a continuous cycle through the gasification zone and associated cyclone and back to the gasification zone, although separately; but simultaneously the fungible or common molten medium also flows in a continuous cycle between the mixed phase carbona- tion zone, the associated cyclone, and the heat exchanger. Also simultaneously, but independently, the molten mass flows between the two closed circuits in a separately.controlled cycle. High sulfur carbonaceous feed enters the mixed phase gasification reaction zone 200 through line 201 in the lower section of said zone. Oxygen-containing gas, steam, if. any, and/or diluting gas,

OMPI if any, enter the lower section of said gasification zone 200 through line 202. In this lower zone of the gasification reactor, molten medium enters through line 203 and mixes with said feed of line 201 and said oxygen-containing gas and steam, if any, and/or diluting gas, if any, to form a multi-phase mixture in the lower section of said gasification zone. The mixed-phase mixture rises through the vertically elongated gasification zone to the upper section of said zone wherein said mixture is transferred to cyclone 208 through line 207. Feed may be introduced into the mixed phase gasification zone either separately in admixture with steam and/or diluting gas, if any. While a cyclone is shown in this preferred example, other separation type devices can also be utilized. In cyclone 208 the gaseous reactants are separated from the liquid consisting of molten medium and the non-gaseous portion of the reactants. The gaseous reactants exit cyclone 208 through line 209 and are directed to downstream separation equipment (not shown) or are used as such. The liquid separated in cyclone 208 settles to the lower portion of the cyclone and is withdrawn through 211 forming an interfacial level 210 which may be maintained in line 211 or the lower portion of cyclone 208. The liquid in line 211 is separated into two portions, with one portion flowing by way of line 204 back to line 203 to complete one of the con¬ tinuous cycles referred to above. Circulation within this closed loop system of molten mass is dependent. upon the location of the interfacial level of liquid 210 and other physical factors of the reactants and equipment. The second portion of liquid contained in l ne 211 flows through line 206 to combine with molten medium

OMPI of line 223 to form a mixture contained in line 212, which then flows to exchanger 213. In exchanger 213 the molten medium is cooled by a fluid such as steam, which enters heat exchanger 213 through line 225 and exits through line 224. The cooled molten medium from heat exchanger 213 flows through line 214 into the lower section of a mixed phase carbonation zone 217. A C0₂ rich gas enters the lower section of the carbonation zone 217 through line 215. Steam, and/or a diluting gas, if any, enters the lower section of said carbona¬ tion zone to form a mixed phase mixture which flows upwardly and co-currently through said carbonation zone to the upper portion thereof. The carbonation zone is sized such that the multi-phase mixture of gases and liquid will create a flow which is sufficiently turbulent that the average density is sufficiently low to create a gas lift effect within the vertically elongated carbonation zone 217. The multi-phase mixture from the upper portion of car¬ bonation zone 217 exits through line 218 and enters the associated cyclone 219. Said multiphase mixture is separated in cyclone 219 into a hydrogen sulfide-rich product gas and a liquid consisting of desulfurized molten medium and liquid or solid reactants. The hydrogen sulfide-rich gas product exits cyclone 219 through line 220 to an external recovery system, such as a Claus type sulfur plant, not shown. The molten medium separated in cyclone 219 settles to the lower section of said cyclone and exits through line 222 and is divided into two portions. The first portion of the desulfurized medium in line 222 passes through line 223 and com- bines with liquid molten medium of line 206 to form an admixture •molten medium in line 212, as previously mentioned. Molten medium 24 ^{' ■ ■} - ^{' ' '}

is thereby circulated in the continuous cycle through heat exchanger 213, carbonation zone 217, and cyclone 219 back to heat exchanger 213 to complete that cycle.

In addition to the two continuous cycle circulation systems of molten medium referred to above, in Figure 2 molten medium from line 222 flows by way of line 205 to combine with molten medium in line 204 which forms the molten medium of l ne 203 referred to above. Therefore, the molten medium flows back and forth between the two reaction systems, whereby a portion of the molten medium from the gasification system flows by way of line 206 to the car¬ bonation reaction system, while an equal quantity of molten medium flows in the opposite direction through line 205 to complete the cycle.

In Figure 2, the pressure maintained in the carbonation reaction zone 217 and associated cyclone 219 is a lower pressure than the pressure maintained in the gasification zone 200 and associated cyclone 208. This is achieved by locating the carbona¬ tion zone 217 and its associated cyclone 219 such that the inter¬ facial level 221 between hydrogensulfide gaseous product and molten medium is at a greater elevation than the interfacial level 210 between the gaseous product of the gasification zone and molten medium. The difference in pressure between these two reaction zones is a function of the difference in interfacial level elevation and other physical factors. In actual operation, the absolute pressure difference may be varied somewhat by adjusting the relative elevation between interfacial level 221 and inter¬ facial level 210. Likewise, the molten medium circulation rate

O - within the gasification zone 200 and associated cyclone 208 may be varied within design limits by raising or lowering the inter¬ facial level 210 (a higher level creating a greater circulation and a lower level causing a Tower circulation rate). Likewise, the circulation rate of molten medium in the cycle between carbon¬ ation zone 217, cyclone 219, and heat exchanger 213 is adjusted within design limits by raising or lowering the interfacial level 221.

In order to control the flow of molten medium back and forth between the two respective reaction zone closed systems through line 206 and line 205, this line is sized so as to limit the flow due to differential static pressure, or alternatively, a restricting line or orifice or.a valve may be incorporated therein. Restrictions or control valves also may be desirable to control flow of molten medium, such as restriction 226 shown in line 205 or restriction 227, shown in line 206. Other flow controlling or restricting equipment will be helpful, particularly if a variety of carbonaceous feeds are to be processed at frequent time intervals. Referring now to Figure 3, there is described a two reaction zone system utilizing the fungible or common molten medium for different reactions in each of the two zones. A carbonaceous feed material enters the lower section of mixed phase cracking reaction zone 10 through line (or conduit) 11. Steam, if any, and/or dilu- ting gas, if any, enters said lower section of the cracking zone 10 through line 12. Feed may be admixed with steam, if any, and/or diluting gas, if any, prior to entering the lower section of said cracking zone 10. Molten medium enters the lower section of said cracking zone 10 through line 13, wherein it mixes with carbonaceous feed and steam if any, and diluting gas, if any, to form a turbu¬ lent mixed-phase mixture which flows co-currently upwardly through the vertically elongated cracking reaction zone 10 to the upper section of said zone. In the upper section of said cracking zone, the mixed-phase consists of gaseous reactants and a liquid com¬ posed of molten medium and/or liquid or solid reactants. Said mixed-phase mixture is transferred from the upper section of said vertically elongated cracking reaction zone 10, through line 14, to a separation device herein identified as a cyclone 15. The gaseous products of the cracking reaction exit from the upper section of cyclone 15 through line 16 for separation and/or use of external equipment, not shown. The liquid portion of material entering cyclone 15 settles to the lower section of said cyclone and exits through line 18 to form an interfacial level 17, which ^' may be maintained in line 18 or in the lower section of cyclone 15. The liquid of line 18 consisting of molten medium and liquid or solid reactants from the cracking reaction zone, flows into line 19 which enters the lower section of the mixed phase oxidation zone 22. An oxygen-containing gas enters the lower section of said mixed phase oxidation zone 22 through line 20. Steam, if any, and/or diluting gas, if any, enter the lower section of said mixed phase oxidation zone 22 through line 2. The oxygen-contain- ing gas may be admixed with steam, if any, and/or diluting gas, if any, prior to introduction to the lower section of said oxidation zone 22. Additional carbonaceous feed material may also be introduced into the lower section of said oxidation zone 22 to supplement any deficiency of liquid or solid reaction products to sustain and heat balance the desired overall system operation. The feed, steam, if any, and diluting gas, if any, mix with the liquid consisting of the molten medium and liquid or solid carbonaceous reactants to form a multi-phase mixture which passes in turbulent flow upwardly through the vertically elongated oxidation reaction zone 22 to the upper portion of said zone. From the upper section of said oxidation zone 22, the mixed-phase mixture is transported by way of line 23 to a separation device, herein identified as cyclone 24, for the separation of vapor phase from liquid phase. The vapor phase consisting of gaseous products of the oxidation reaction exits cyclone 24 through line 25. for use or separation externally. The liquid separated in cyclone 24, consisting of molten medium and any liquid or solid reactants, collects in the lower section of said cyclone 24 and exits through line 27 to form an interfacial level 26. The inter¬ facial level 26 may be maintained in line 27 or in the lower sec¬ tion of cyclone 24. Line 27 flows into line 13, through which molten medium completes the cycle by returning to the lower section of cracking zone 10. The pressure of the oxidation zone 22 and associated cyclone 24 may be maintained at a pressure different from the cracking zone 10 and its associated cyclone 15 by de¬ signing the equipment so that interfacial level 26 is different from interfacial level 17. By increasing or decreasing the inventory of molten medium, this raising or lowering both interfacial levels simultaneously, one may increase or .decrease the circulation rate

OMPI ^" ΪPO of. molten medium throughout the system (raising both interfacial levels causing an increase in circulation rate - lowering both interfacial levels creating decreased circulation rate of molten medium). Reference is now made to Figure 4, which differs from Figure 3 only in that line 28 and valve or restriction 29 have been added. The addition of these two items is to facilitate some independent control of the circulation rate of molten medium through one or more reaction zones independent of the overall circulation rate between respective reaction zones. In Figure 4, the liquid from cyclone 24, consisting of molten medium and any unreacted liquid or solid reactants, is separated into two portions as follows: one portion flows through line 28 and re¬ striction 29 to combine with the molten medium and liquid or solid reactants in line 18, after which the two streams admix in line 19, from said line 19 the admixture flows into the lower section of the oxidation zone 22; the second portion flows to line 13, as described in connection with Figure 3. The two independent molten streams meeting and mixing in line 19 could alternately be intro- duced into the lower section of said oxidation zone 22 independently. Restriction 29 can consist of a line sized so as to not permit a flow greater than that desired, or it may be a fixed restriction such as an orifice, or a control valve. The addition of line 28 and restriction 29 permits control of the circulation rate of molten medium through oxidation zone 22 and its associated cyclone 24 somewhat independently of the circulation rate in the cracking zone 10 and its associated cyclone 15. Referring to Figure 5, there is disclosed a system having three separate reaction zones for independently conducting three separate chemical reactions simultaneously, utilizing a fungible or common molten mass medium. This specific example differs from that illustrated in Figure 3, in that a portion of the molten medium is withdrawn after the oxidation reaction and is used as the reaction medium for conducting the third chemical reaction, and the molten medium, after being used as the medium in the third chemical reaction, is returned to the oxidation zone from which it came. Alternatively, the molten medium from the third chemical reaction, e.g., carbonation, could be returned instead to the cracking reaction zone. Referring to Figure 5, a carbona¬ ceous feed material such as, but not limited to, asphalt enters the lower section of the mixed phase cracking zone 100 through line 101. Steam, if any, and/or diluting gas, if any, enters the lower section of said cracking reaction zone 100 through line 102. Molten medium enters the lower section of the cracking reaction zone 100 by way of line 103, and it mixes with feed and steam, if any, and/or diluting gas, if any, in the lower section of said cracking zone 100. The mixed phase fluid rises through the vertically elongated cracking zone 100 to the upper portion thereof. From the upper section of cracking zone 100 the multi-phase mix¬ ture of gas and liquid flows by way of line 104 to a separation device identified as cyclone 105. In cyclone 105, the gaseous products of the cracking reaction exit through line 106 to external recovery and/or use equipment, not shown. The liquid of cyclone 105, consisting of molten medium and liquid or solid reactants,

OMPI is separated and settles to the lower section of cyclone 105 from which it exits through line 108 to form an interfacial level 107, which may be maintained in line 108 or in the lower section of cyclone 105. The molten liquid of line 108 combines with molten medium from line 131 (to be described later) to form an admixture in line 109 which enters the lower section of the mixed phase oxidation zone 112. An oxygen-containing stream is introduced into the lower section of the oxidation reaction zone 112 through line 110. Steam, if any, and/or diluting gas, if any, enters the lower section of the oxidation reaction zone 112 through line 111. The molten medium of line 109 combines and mixes with the oxygen containing gas of line 110 and steam, if any, and/or diluting gas, if any, entering through line 111 to form a multi-phase mixture in the lower section of said oxidation zone 112. This multi-phase mixture rises in turbulent co-current flow to the upper section of said oxidation zone 112. From the upper section of said oxi¬ dation zone 112, the multi-phase mixture flows by way of line 113 to an associated separation device identified as cyclone 114, wherein the gaseous reaction products of the oxidation reaction separate from liquid consisting of molten medium and liquid or solid reactants. The gaseous reaction products of the oxidation reaction exit cyclone 114 through line 115 for separation and/or use externally. The liquid, consisting of molten medium and liquid or solid reactants, settles to the lower section of cyclone 114 from which it exits said cyclone through line 117 to form an inter¬ facial level 116, which may be maintained in line 117 or in the lower section of cyclone 114. The liquid of line 117 is divided into two portions, whereupon one portion flows by way of line 103 back to the lower section of the cracking zone 100. The second portion of the liquid in line 117 flows by way of line 118 to a heat exchanger 119, wherein the temperature of the molten medium is reduced by heating a fluid, such as a circulated oil which flows into heat exchanger 119 through line 120 and exits said heat ex¬ changer by way of line 121. The thus-cooled molten medium of line 118, after passing through heat exchanger 119, flows to the lower section of the carbonation reaction zone 125 by way of line 124. A carbon dioxide-rich gas enters the carbonation reaction zone 125 by way of line 123. Steam and diluting gas, if any, enter the lower section of the mixed-phase carbonation zone 125 by way of line 122. Alternatively, it is possible to introduce the carbon dioxide-rich gas and/or steam and/or diluting gas into the molten medium in line 118 before said molten medium enters heat exchanger 119. The molten medium mixes with carbon dioxide-rich gas and steam and diluting gas, if any, in the lower section of the carbon¬ ation zone 125 to form a multi-phase mixture which rises through the vertically elongated carbonation reaction zone 125 to the upper section of said zone. From the upper section of said carbonation zone, the multi-phase mixture of gaseous reactants and liquid flows by way of line 126 to a separation device identified as cyclone 127. From cyclone 127, the gaseous products, consisting of a hydrogen sulfide-rich gas, exit cyclone -127 through line 128 for further processing such as in a Claus type plant (not shown) to form elemental sulfur or to be used externally. The liquid entering cyclone 127, consisting of molten medium and unreacted liquid or solid reactants, settles to the lower section of said cyclone 127 and exits by way of line 130 to form an interfacial level 129, which may be maintained in line 130 or in the lower section of cyclone 127. The liquid in line 130, which in Figure 5 becomes line 131, returns to mix with the liquid of line 108 to flow through l ne 108 back to the lower section of the oxida¬ tion zone 112 as previously mentioned.

While still referring to Figure 5^' but as was shown in Figure 4, the liquid line 130 could alternatively be divided into two portions, with one portion flowing as shown through line 131 back to the oxidation zone, and the second portion flowing by the way of a line (not shown) back to line 118 to recycle through the carbonation zone 125 with an appropriate restriction or valve, if desired, as described in connection with Figure 4. In each of the embodiments illustrated in Figures 1-5, the mixed phase reaction zones are designed so that the multi-phase mixtures will create a co-current flow with such a velocity that the average density within said zones will create a gas lift effect and cause circulation of the molten medium. It will be appreciated, however, that the second and/or third stage reaction zones need not be designed and/or operated in this manner in order for each of the illustrated embodiments, as a whole, to fall within the scope of the present invention.

Optionally, in each of the illustrated embodiments the stream of molten mass medium exiting from the separation device (cyclones) for recirculation may be subjected to a second or sub¬ sequent separation treatment in order to further separate any gases dissolved therein. Such a second separation step may take the form of a second separation device, such as a cyclone, or alter¬ natively, the molten mass medium may be contacted with a stripping agent, such as a stripping gas. Such a stripping gas can also be used concurrently with a second cyclone. Example 1

A high sulfur-content asphalt is cracked to produce ethylene by the process described with reference to Figure 3. The molten mass comprises a eutectic mixture of lithium, potassium, and sodium carbonates, in which an alkali metal sulfide concentration of about 5% by weight is maintained. The asphalt feed is first preheated to a temperature of about 250°C, and is then contacted with the molten mass in the lower portion of the reaction zone such that the upward velocity is in the range of 10 to 100 ft/second, pre- ferably 20 to 40 ft/second. Steam and/or diluting gas may also be introduced into the lower portion of the cracking zone, and is taken into consideration in determining the upward velocity. The circulation rate of the molten mass is maintained at between 1 and 15 pounds of mass per pound of total feed including steam and diluting gas in addition to asphalt to establish, under steady- state operating conditions, a froth flow transport condition in the cracking reaction zone, and a total contact time between reac¬ tants and molten salt of about 1 to 10, preferably about 2 seconds. The processing capacity and ethylene yields of the instant process are then compared with the conventional prior art molten mass cracking process, such as that described in U. S. Patent No. 3,745,109. All other reaction conditions are maintained at similar values in each process, with the temperature being maintained at about 850°C. and the pressure being maintained at about 1.3 atmospheres absolute in each cracking zone. In contra¬ distinction to the instant invention, the prior art countercurrent flow cracking process possesses feed rates approximately 1/10 that utilized in the instant invention, and contact times approximately 3 to 5 times longer than those utilized in the instant invention. Example 2

Similarly to Example 1, a heavy hydrocarbon residium produced by distillation is satisfied according to the process described with reference to Figure 1, and the results are compared with those obtained from a conventional countercurrent flow gasification reaction. Each reaction zone is maintained with a temperature of about 1000°C and a pressure of about 1.5 to 15.0 atmospheres. Oxygen-containing gas (air) and steam are introduced into the reaction zone with a steam to oxygen weight ratio of about 0.3 to 5.0 pounds H2O vapor to each pound of oxygen depending on heat losses and oxygen purity. The feed rate of the hydrocarbon residium and oxygen-containing gas, and steam in the process of the present invention is adjusted to establish under steady-state operating conditions a froth flow transport condition within the reaction zone, and comprises about 10 to 100 ft/second, preferably 20 to 40 ft/second. In contrast, in order to maintain a countercurrent flow between molten medium and hydrocarbon residium in the process of the prior art, the feed rate of hydrocarbon residium feed and oxygen-containing gas, and steam is maintained at about 2.0 feet per second therein.. The aforementioned feed rates are sufficient to establish contact times of about 0.5 seconds in the process of the instant invention, and contact times of about 3 to 5 seconds in the prior art gasification process. Comparison of the two processes reveals that much greater amounts of hydrocarbon residium, on the order of about 10 times as much, can be processed by the process of the instant invention than can be processed by the countercurrent flow process of the prior art, and due to the larger size of equipment required by prior art, the percentages of total heat lost through vessel walls is about 4 times greater. It is thus seen from the foregoing examples that by con¬ tacting a hydrocarbonaceous feed material with the molten medium with a multi-phase co-current froth flow transport, a significant increase in processing capacity is accrued, a processing capacity which for the first time enables competitive, commercial use of molten mass technology in the conversion of hydrocarbonaceous feed materials. Moreover, due to the much lower contact times possible therein improved product yields are possible in many reactions. Accordingly, the present invention provides an improved and highly efficacious method for the conversion of carbonaceous feed materials.

While the invention has been described in terms of pre¬ ferred embodiments, and illustrated by examples, various modifica¬ tions, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be defined solely by the scope of the following claims.

Claims

1. A molten mass medium process for the conversion of a carbonaceous feed material into more valuable products, comprising the steps of: a) contacting a carbonaceous feed material with a molten mass medium maintained at a temperature above the melting point of said medium in the lower section of a substantially vertical elongated reaction zone to form a mixture of carbonaceous feed material and molten mass medium, whereby at least one gaseous material is present under the conditions of said reaction zone and a multi-phase mixture is formed; b) hydraulically transporting said multi-phase mixture substantially upwardly through said reaction zone to the upper section thereof with a co-current flow of the components of said mixture, and with a velocity sufficient to establish a gas lift effect in said reaction zone, whereby a chemical conversion reaction takes place to produce a multi-component mixture; c) passing the multi-component mixture from the upper section of said reaction zone to a separation device; d) separating the multi-component mixture into a gaseous product stream and a liquid stream comprising said molten mass medium containing at least one nongaseous product; e) passing at least a portion of said liquid stream of molten mass medium containing a nongaseous product to a recovery section; f) removing at least a portion of the said nongaseous product from said liquid stream of molten mass medium; and

f OM g) returning the molten mass medium from which at least a portion of the nongaseous product has been removed back to said vertical, elongated reaction zone.

2. The process of Claim 1, further comprising the step of recycling the remainder of said separated liquid stream of molten mass medium back into said lower section of said reaction zone.

3. The process of Claim 2, further comprising the step of introducing a gaseous reactant into the lower section of said vertical, elongated reaction zone.

^• 4. The process of Claim 2, wherein said gaseous reactant is selected from the group consisting of an oxygen-containing gas, steam, halogen, light hydrocarbon, hydrogen or mixtures thereof.

5. The process of Claim 2, further comprising the step of introducing a diluting gas into the lower section of said vertical elongated reaction zone.

6. The process of Claim 5, wherein said diluting gas comprises nitrogen or steam.

7. The process of Claim 2, further .comprising the step of subjecting said gaseous product stream to an additional gas-liquid separation step to recover additional molten mass medium entrained therewith.

8. The process of Claim 2, further comprising the step of contacting said separated liquid stream of molten mass medium with a stripping gas in order to remove dissolved gas therefrom.

9. The process of Claim 2, wherein said carbonaceous feed material conversion reaction comprises the cracking of a less valuable carbonaceous feed material at least partially into a more valuable gaseous hydrocarbon product.

10. The process of Claim 2, wherein said carbonaceous feed material is selected from the group consisting of vegetable and mineral oils, crude oils, shale oil, natural tars, coal, pitch, tar sand oils, the fractions, residiums, products, polymers, resins, synthetic tars and waste thereof; and mixtures thereof.

11. The process of Claim 9, wherein said lower-value hydrocarbon feed material is an asphalt or a hydrocarbon residium produced by distillation or distillation and solvent extraction of crude oil shale oil, tar sand oils, or coal liquid.

12. The process of Claim 2, wherein said carbonaceous feed material comprises rubber, carbon black, lubricating oils; the waste or fractions thereof; or a combination thereof.

13. The process of Claim 2, wherein said carbonaceous feed conversion reaction comprises the partial oxidation of a less valuable carbonaceous feed material into a more valuable gas.

14. The process of Claim 13, wherein said carbonaceous feed conversion reaction comprises the partial oxidation of coke.

15. The process of Claim 1, wherein at least a portion of said separated liquid stream of molten mass medium is treated to remove a portion of its sulfur content prior to returning said molten medium to said reaction zone.

16. The process of Claim 15, wherein the sulfur content of said molten mass medium is reduced by contacting said molten mass medium with carbon dioxide and steam to chemically convert the alkal metal-sulfur compounds present therein into alkali metal carbonates and hydrogen sulfide gas, and then separating said hydrogen sulfide gas from said molten mass medium.

17. The process of Claim 15 or 16, wherein the molten mass medium also contains a carbon or carbonaceous material content and said carbon or carbonaceous material content remains present throughout said treating.

18. The process of Claim 15, wherein the amount of said molten mass medium subjected to said sulfur-removal step is of sufficient portion such that under steady-state operating conditions the amount of sulfur compounds present in said molten mass medium is maintained below about 25% by weight thereof.

19. The process of Claim 1, further comprising the step of transferring heat relative to said portion of said separated liquid stream of molten mass medium.

20. The process of Claim 19, wherein the nongaseous product content of said portion of said separated liquid stream of molten mass medium is treated by the steps of: ^~" a) feeding said portion of said separated liquid stream of molten mass medium into the lower section of a second substan¬ tially vertical elongated reaction zone; b) contacting said separated liquid stream of molten mass medium with a carbon dioxide and steam-containing gas to form a second mult -phase mixture; c) hydraulically transporting said second multi-phase mixture of carbon dioxide and steam-containing gas and molten mass medium upwardly through said second reaction zone to the upper section thereof with a co-current flow of gas and liquid in order to carbonate said nongaseous product, said second multi-phase mixture being transported with a velocity sufficient to establish a gas lift effect in said second reaction zone; d) passing said second multi-phase mixture from the said upper section of said second reaction zone to a second separation device; and e) separating said second multi-phase mixture into a second gaseous product stream and a second liquid stream of reduced, nongaseous product content molten mass medium.

21. The process of Claim 19, wherein the amount of said portion of said separated liquid stream of molten mass medium subjected to said treating steps is of a proportion sufficient to maintain a steady state balance of the sulfur content of said process in continuous operation.

22. The process of Claim 2 or 9, wherein said molten mass medium comprises an alkali metal selected from the group consisting of sodium, potassium, lithium, the carbonates thereof, the sulfides thereof, the sulfates thereof, the sulfites thereof, the chlorides thereof, and mixtures thereof.

23. The process of Claim 22, wherein said molten mass medium comprises an alkali metal carbonate, an alkali metal sulfide, or a mixture thereof.

24. The process of Claim 1, 9 or 13, wherein the transport velocity of said multi-phase mixture is such that the total contact time between said carbonaceous feed material and said molten mass medium is less than about three seconds.

25. The process of Claim 24, wherein said contact time is less than about one second.

26. The process of Claim 1, wherein said molten mass medium comprises an elemental metal, a mixture of elemental metals, a metal salt, a mixture of metal salts and a mixture of metal salt and elemental metal.

27. The process of Claim 26, wherein said molten mass medium comprises an alkali metal, a mixture of alkali metals, an alkali metal salt, a mixture of alkali metal salts, or a mixture of an alkali metal and an alkali metal salt.

28. The process of Claim 1, wherein the process is operated in continuous manner.

29 The process of Claim 1, wherein the process is operated wiithout the use of a mechanical pump.

30. A closed cycle molten mass medium process for the conver¬ sion of a carbonaceous feed material into more valuable products comprising the steps of: a) contacting a carbonaceous feed material with a first molten mass medium maintained at a temperature above the melting point of said medium in the first lower section of a substantially vertical, elongated first reaction zone to form a mixture of car¬ bonaceous feed material and molten mass medium, whereby at least one gaseous material is present under the conditions of said first reaction zone and a first multi-phase mixture is formed; b) hydraulically transporting said first multi-phase mixture substantially upwardly through said first reaction zone to the first upper portion thereof with a co-current flow of the components of said first mixture, and with a velocity sufficient to establish a gas lift effect in said first reaction zone; c) passing said first multi-phase mixture from the said first upper section of said first reaction zone to a first separation device; d) separating said first multi-phase mixture into a first gaseous product stream and a first liquid stream comprising said molten mass medium; e) feeding at least a portion of said first liquid stream into the lower section of a second substantially vertical elongated reaction zone to -form a second multi-phase mixture within said lower section, whereby at least one gaseous material is present under the conditions of said second reaction zone; f) hydraulically transporting said second multi-phase mixture substantially upwardly through said second reaction zone to the second upper portion thereof with a co-current flow of the components of said second multi-phase mixture, and with a velocity sufficient to establish a gas lift effect in said second reaction zone; g) passing said second multi-phase mixture from the said second upper section of said second reaction zone to a second separation device; h) separating said second multi-phase mixture into a second gaseous product stream and a second liquid stream comprising molten mass medium; and i) feeding at least a portion of said second liquid stream containing molten mass medium to the lower section of said first reaction zone.

31. The process of Claim 30, wherein the chemical version of said first reaction zone comprises a cracking reaction.

32. The process of Claim 30 or 31, whrein the second chemical reaction comprises at least a partial oxidation reaction wherein the oxygen of an oxygen-containing gas is reacted with reactants contained in the said first liquid stream.

33. The process of Claim 30, further comprising the steps of feeding at least a portion of said second liquid stream to a third reaction zone, and contracting said second liquid stream with carbon dioxide and steam to adjust the concentration of the sulfur compounds present therein and to remove a portion of the sulfur content of said molten mass medium as a hydrogen sulfide-rich gas.

34. The process of Claim 30, further comprising the steps of feeding at least a portion of said first liquid stream to a third reaction zone, and contacting said first liquid stream with carbon dioxide and steam to adjust the concentration of the sulfur compounds present therein and to remove a portion of the sulfur content of said molten mass medium as a hydrogen sulfide-rich gas.

35. A process according to Claim 30, wherein said first liquid stream is contacted with an oxygen containing gas in said second reaction zone to at least partially oxidize carbonaceous reactants present in said first liquid stream.

36. The process of Claim 33 or 34, wherein said sulfur adjust¬ ment step occurs subsequent to cooling of said first liquid stream.

37. The process of Claim 1 or 30, wherein said carbonaceous feed material is selected from the group consisting of crude oil, shale oil, natural tars, coal, pitch, tar sand oils, the fractions, residium, products, polymers, resins, synthetic tars, and waste thereof, and mixtures thereof.

38. The process of Claim 37, wherein said feed material is an asphalt or a hydrocarbon residium produced by distillation and solvent extraction of crude oil.

39. The process of Claim 1 or 30, wherein said molten mass medium contains a catalytic material admixed therewith.

40. The process of Claim 39, wherein said molten mass medium contains from about 0 to 50% by weight of^'said catalytic material.

41. The process of Claim 39, wherein said molten mass medium contains from about 10% to 25% by weight of said catalytic material.

42. The process of Claim 30, wherein said molten mass medium is a mixture of alkali metal (s) selected from the group consisting of sodium, potassium, lithium, the carbonates thereof, the sulfides thereof, the chlorides thereof, the sulfates thereof, the sulfites thereof, or mixtures thereof.

1TU E4 >

OMPI

43. The process of Claim 30, wherein the transport velocity of said first multi-phase mixture in said first reaction zone is such that the total contact time between said feed and said molten mass medium is less than about 5 seconds.

44. The process of Claim 30, wherein said conversion reaction comprises at least a gasification reaction wherein a carbonaceous feed material is converted to a low or medium BTU gas.

45. The process of Claim 30, wherein said conversion reaction comprises a dehydrogenation reaction.

46. The process of Claim 30, wherein said conversion reaction comprises the dehydrogenation of ethyl benzene.

47. The process of Claim 30, wherein said conversion reaction comprises the reforming of naphtha.

48. The process of Claim 13 or 30, wherein said carbonaceous feed material conversion reaction comprises the gasification of coal, asphalt, cycle oil, tar sand oil, shale oil, or hydrocarbon residiums.

__OMPI IPO

49. The process of Claim 30, wherein said second reaction treatment of said molten mass medium comprises a sulfur content adjustment step wherein said molten mass medium is contacted with carbon dioxide and steam to convert a portion of the sulfur compounds present therein to hydrogen sulfide-rich gas.

50. The process of Claim 49, wherein the molten mass medium also contains a carbon or carbonaceous material content and said carbon or carbonaceous material content remains present throughout said sulfur content adjustment step.

51. The process of Claim 49, wherein said sulfur content of said molten mass medium is adjusted such that said molten mass medium comprises less than about 25% by weight sulfur compounds.

52. The process of Claim 30, wherein said molten mass medium ^' is circulated between said reaction zones without the aid of a pump.

53. The process of Claim 30, wherein each said separation step comprises cyclonically^" separating said gaseous product and said molten mass.

54. The process of Claim 30, further comprising the step of independently controlling the ratio of said molten mass medium to the material to be reached in each of said first and second reaction zones.

55. A process of Claim 30, wherein said first reaction zone is maintained at a pressure different from that of said second reaction zone.

__ OM V^<λ ~WΪP

56. A closed cycle molten mass medium apparatus for the conver¬ sion of a carbonaceous feed material into more valuable products, comprising: a) means for contacting a carbonaceous feed material with a first molten mass medium maintained at a temperature above the melting point of said medium in the first lower section of a sub¬ stantially vertical, elongated first reaction zone to form a mixture of carbonaceous feed material and molten mass medium, whereby at least one gaseous material is present under the conditions of said first reaction zone and a first multi-phase mixture is formed. b) means for hydraulically transporting said first multi¬ phase mixture substantially upwardly through said first reaction zone to the first upper portion thereof with a co-current flow of the components of said first mixture, and with a velocity sufficient to establish a gas lift effect in said first reaction zone; c) means for passing said first multi-phase mixture from the said first upper section of said first reaction zone to a first separation device; d) means for separating said first multi-phase mixture into a first gaseous product stream and first liquid stream com¬ prising said molten mass medium; e) means for feeding at least a portion of said first liquid stream to a second reaction zone; f) means for conducting a second chemical reaction in the molten mass medium of said first liquid stream in said second reaction zone; and g) means for recycling at least a portion of said molten mass medium from the said second reaction zone back into said first lower section of said first reaction zone.

57. The apparatus of Claim 56, comprising: a) means for contacting at least a portion of said first liquid stream containing said molten mass medium with an oxygen- containing gas in the second lower section of the second sub- stantially vertical, elongated reaction zone to form a second multi-phase mixture within said lower section, whereby at least one gaseous material is present under the conditions of said second reaction zone; b) means for hydraulically transporting said second multi-phase mixture substantially upwardly through said second reaction zone to the second upper portion thereof with a co-current flow of the components of said second multi-phase mixture, and with a velocity sufficient to establish a gas lift effect in said second reaction zone; c) means for passing said second multi-phase mixture from the said second upper section of said second reaction zone to a second separation device; d) means for separating said second multi-phase mixture into a second gaseous product stream and a second liquid stream comprising molten mass medium; and e) means for feeding at least a portion of said second liquid stream containing molten mass medium to the said first lower section of said first reaction zone.

58. The apparatus of Claim 57, further comprising means for feeding at least a portion of said second liquid stream to a third reaction zone, and means for contacting said liquid stream with carbon dioxide and steam to adjust the concentration of the sulfur compounds present therein and to remove a portion of the sulfur content of said molten mass medium as a hydrogen sulfide- rich gas.

59. The apparatus of Claim 57, further comprising means for feeding at least a portion of said first liquid stream to a third reaction zone, and means for contacting said first liquid stream with carbon dioxide and steam to adjust the concentration of the sulfur compounds present therein and to remove a portion of the sulfur content of said molten mass medium as a hydrogen sulfide-rich gas.

60. The apparatus of Claim 58 or 59, wherein said contacting means for sulfur adjustment is subsequent to a cooling means for said third reaction zone.

61. A molten mass medium process for the conversion of a carbonaceous feed material into other products, comprising the steps of: a) contacting a carbonaceous feed material with a molten mass medium maintained at a temperature above the melting point ofsaid medium in the lower section of a substantially vertical, elongated reaction zone to form a mixture of carbon¬ aceous feed material and molten mass medium, whereby at least one gaseous material is present under the conditions of said reaction zone and a multi-phase mixture is formed; b) hydraulically transporting said multiphase mixture substantially upwardly through said reaction zone to the upper section thereof with a co-current flow of the components of said mixture, and with a velocity sufficient to establish a gas lift effect insaid reaction zone, whereby the hydrocarbon feed reacts chemically to produce a multi-component mixture; c) passing the multi-component mixture from the upper section of said reaction zone to a separation device; and d) separating the multi-component mixture into a gaseous product stream and a liquid stream comprising said molten mass medium; wherein all reactants introduced into said molten mass medium flow co-currently with said medium, and the gaseous reaction products separate from said multi-phase mixture without passing through a liquid interface.

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