Improved integrated coking-gasification process with mitigation of slagging

Abstract

A fluid coking-gasification process for converting heavy hydrocarbonaceous chargestocks to lower boiling products in which an inorganic metal composition is used to mitigate slagging in the gasifier, wherein the metal is selected from the alkaline-earths, the rare earths, and zirconium. The inorganic metal composition is added either directly into the gasifier or it is mixed with the coke passing from the heating zone to the gasification zone.

Description

FIELD OF THE INVENTION

The present invention relates to an improved integrated fluid coking-gasification process wherein an inorganic metal composition is used to mitigate slagging in the gasifier. The metal of the inorganic composition is selected from the group consisting of the alkaline-earth metal, the rare earths, and zirconium.

BACKGROUND OF THE INVENTION

Much work has been done over the years to convert heavy hydrocarbonaceous materials to more valuable lighter boiling products. One such process is an integrated fluid coking-gasification process in which a heavy hydrocarbonaceous chargestock is fed to a coking zone comprised of a fluidized bed of hot solid particles, usually coke particles, sometimes referred to as seed coke. The heavy hydrocarbonaceous material is reacted in the coking zone resulting in conversion products which include a vapor fraction and coke. The coke is deposited on the surface of the seed particles. A portion of the cokedseed particles is sent to a heater which is maintained at a temperature higher than that of the coking zone where some of the coke is burned off. Hot seed particles from the heater are returned to the coking zone as regenerated seed material which serves as the primary heat source for the coking zone. Coke from the heating zone is circulated to and from a gasification zone which is maintained at a temperature greater than the heating zone. In the gasifier, substantially all of the coke which was laid-down on the seed material in the coking zone, and which was not already burned-off in the heating zone, is burned, or gasified, off. Some U.S. Patents which teach an integrated fluid coking-gasification process are U.S. Pat. Nos. 3,726,791; 4,203,759; 4,213,848; and 4,269,696; all of which are incorporated herein by reference.

Myriad process modifications have been made over the years in fluid coking in an attempt to achieve higher liquid yields. For example, U.S. Pat. No. 4,378,288 discloses a method for increasing coker distillate yield in a thermal coking process by adding small amounts of a free radical inhibitor.

Also, U.S. Pat. No. 4,642,175 discloses a method for reducing the coking tendency of heavy hydrocarbon feedstocks in a non-hydrogenative catalytic cracking process by treating the feedstock with a free radical-removing catalyst so as to reduce the free radical concentration of the feedstock.

A problem which is being increasingly encountered is slagging in the gasifier of an integrated fluid coking-gasification commercial unit. Slagging is a complex phenomenon which is influenced by many factors and which can be a cause of major operability problems. For example, the formation of significant amounts of slag can cause blockage of the grid assembly in the gasifier. The grid assembly is comprised of inlet pipes for the introduction of steam and the oxygen-containing gas, and it is located at the bottom of the gasifier. Blockage of this grid assembly will increase the pressure and have an adverse effect on the flow distribution in the bed. If the blockage becomes excessive, design gasification rates may not be achievable and/or run lengths may have to be reduced. Slags can also corrode the cap materials of the grid assembly and form even larger slag accumulations. It is believed that the presence and build-up of high melting vanadium salts in the gasifier are the chief cause of slagging. Consequently, there exist a need in the art for ways to mitigate slagging problems.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided an improved integrated fluid coking-gasification process for converting heavy hydrocarbonaceous feedstocks to lower boiling products. The process comprises:

(a) introducing a heavy hydrocarbonaceous chargestock into a coking zone comprised of a bed of fluidized solids maintained at fluid coking conditions, including a temperature from about 850.degree. to 1200.degree. F. and a total pressure of up to about 150 psig, to produce a vapor phase product including normally liquid hydrocarbons, and coke, the coke depositing on the fluidized solids;

(b) introducing a portion of said solids, with coke deposited thereon into a heating zone comprised of a fluidized bed of solid particles and operated at a temperature greater than said coking zone; and

(c) recycling a portion of said heated solids from said heating zone to said coking zone;

(d) introducing a second portion of said heated solids from the heating zone to a gasification zone comprised of a fluidized bed of solid particles and maintained at a temperature greater than said heating zone; and

(e) reacting said second portion of heated solids in said gasification zone with steam and an oxygen-containing gas;

wherein an effective amount of an inorganic metal composition is used as an additive to prevent slagging of the gasifier by: (i) adding it at the bottom of the gasifier of the gasification zone; or (ii) mixing it with the portion of heated solids passing from the heating zone to the gasification zone.

In a preferred embodiment of the present invention the amount of inorganic metal composition used is such that the molar ratio of metal of the composition to vanadium in the feed is from about 0.5 to 1 to about 10 to 1.

In another preferred embodiment of the present invention, the inorganic metal composition is added at the bottom of the gasifier.

In still other preferred embodiments of the present invention, the metal of the inorganic composition is selected from the group consisting of alkaline-earth metals, the rare earths, and zirconium.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 hereof is a schematic flow plan of one embodiment of the present invention for practicing an integrated coking gasification process showing points where the inorganic metal composition can be introduced into the process unit.

FIG. 2 hereof is a graphical representation of slag reduction versus the concentration of representative inorganic compositions of the present invention, for Example 2 hereof.

FIG. 3 hereof is a graphical representation of slag reduction versus concentration of limestone used to mitigate slagging in accordance with Example 2 hereof.

FIG. 4 hereof is a graphical representation of slag reduction versus concentration of limestone in accordance with Example 3 hereof.

DETAILED DESCRIPTION OF THE INVENTION

Any heavy hydrocarbonaceous material typically used in a coking process can be used herein. Generally, the heavy hydrocarbonaceous material will have a Conradson carbon residue of about 5 to 40 wt. % and be comprised of moieties, the majority of which boil above about 975.degree. F. Suitable hydrocarbonaceous materials include heavy and reduced petroleum crudes, petroleum atmospheric distillation bottoms, petroleum vacuum distillation bottoms, pitch, asphalt, bitumen, liquid products derived from coal liquefaction processes, including coal liquefaction bottoms, and mixtures thereof.

A typical heavy hydrocarbonaceous chargestock suitable for the practice of the present invention will have a composition and properties within the ranges set forth below.

______________________________________Conradson Carbon 5 to 40 wt. %Sulfur 1.5 to 8 wt. %Hydrogen 9 to 11 wt. %Nitrogen 0.2 to 2 wt. %Carbon 80 to 86 wt. %Metals 1 to 2000 wppmBoiling Point 340.degree. C.+ to 650.degree. C.+Specific Gravity -10 to 35.degree. API______________________________________

With reference now to FIG. 1 hereof, which shows an integrated fluid coking/gasification unit where most of the coke is gasified with a mixture of steam and air. The reaction vessel is similar for a fluid coking process as it is for an integrated coking/gasification process. In the figure, a heavy hydrocarbonaceous chargestock is passed by line 10 into coking zone 12 in which is maintained a fluidized bed of solids having an upper level indicated at 14. Although it is preferred that the solids, or seed material, be coke particles, they may also be other refractory materials such as those selected from the group consisting of silica, alumina, zirconia, magnesia, alumdum or mullite, synthetically prepared or naturally occurring material such as pumice, clay, kieselguhr, diatomaceous earth, bauxite, and the like. The solids will have an average particle size of about 40 to 1000 microns, preferably from about 40 to 400 microns.

A fluidizing gas e.g. steam, is admitted at the base of coker reactor 1, through line 16, in an amount sufficient to obtained superficial fluidizing velocity in the range of about 0.5 to 5 feet/second. Coke at a temperature above the coking temperature, for example, at a temperature from about 100.degree. to 400.degree. F., preferably from about 150.degree. to 350.degree. F., and more preferably from about 150.degree. to 250.degree. F., in excess of the actual operating temperature of the coking zone is admitted to reactor 1 by line 42 in an amount sufficient to maintain the coking temperature in the range of about 850.degree. to 1200.degree. F. The pressure in the coking zone is maintained in the range of about 0 to 150 psig, preferably in the range of about 5 to 45 psig. The lower portion of the coking reactor serves as a stripping zone to remove occluded hydrocarbons from the coke. A stream of coke is withdrawn from the stripping zone by line 18 and circulated to heater 2. Conversion products are passed through cyclone 20 to remove entrained solids which returned to coking zone through dipleg 22. The vapors leave the cyclone through line 24, and pass into a scrubber 25 mounted on the coking reactor. If desired, a stream of heavy materials condensed in the scrubber may be recycled to the coking reactor via line 26. The coker conversion products are removed from the scrubber 25 via line 28 for fractionation in a conventional manner. In heater 2, stripped coke from coking reactor 1 (cold coke) is introduced by line 18 to a fluid bed of hot coke having an upper level indicated at 30. The bed is partially heated by passing a fuel gas into the heater by line 32. Supplementary heat is supplied to the heater by coke circulating from gasifier 3 through line 34. The gaseous effluent of the heater, including entrained solids, passes through a cyclone which may be a first cyclone 36 and a second cyclone 38 wherein the separation of the larger entrained solids occur. The separated larger solids are returned to the heater bed via the respective cyclone diplegs 39. The heated gaseous effluent which contains entrained solids is removed from heater 2 via line 40.

A portion of hot coke is removed from the fluidized bed in heater 2 and recycled to coking reactor by line 42 to supply heat thereto. Another portion of coke is removed from heater 2 and passed by line 44 to a gasification zone 46 in gasifier 3 in which is maintained a bed of fluidized coke having a level indicated at 48. If desired, a purged stream of coke may be removed from heater 2 by line 50.

The gasification zone is maintained at a temperature ranging from about 1600.degree. to 2000.degree. F. at a pressure ranging from about 0 to 150 psig, preferably at a pressure ranging from about 25 to about 45 psig. Steam by line 52, and a molecular oxygen-containing gas, such as air, commercial oxygen, or air enriched with oxygen by line 54 pass via line 56 into gasifier 3. The reaction of the coke particles in the gasification zone with the steam and the oxygen-containing gas produces a hydrogen and carbon monoxide-containing fuel gas. The gasified product gas, which may further contain some entrained solids, is removed overhead from gasifier 3 by line 32 and introduced into heater 2 to provide a portion of the required heat as previously described.

There is a grid assembly 58 at the bottom of the gasifier which is comprised of inlet pipes for the introduction of steam and the oxygen-containing gas. During normal operation of the gasifier, slag deposits on the grid assembly, which corrodes the grid cap materials and in turn forms larger slag accumulations. The plugged grid caps reduce the available open area and consequently increase grid pressure drop and affects the flow distribution in the bed. If the amount of grid cap plugging, becomes excessive, design gasification rates may not be achievable and/or run lengths may have to be reduced. The vanadium in the coke is considered the contaminant most likely to promote slag formation. For example, vanadium pentoxide has a low melting point relative to the operating temperature of commercial gasifiers. Sodium is another likely contaminant; however, its concentration in gasifier coke is generally low compared to vanadium. The addition of slag mitigation additives to the bottom of the gasifier provides scouring action which would physically attrite and remove some of the slag formed on the grid assembly at the bottom of the gasifier. This benefit would not be available if the additives were introduced at another stage, such as the coking zone.

Inorganic metal compositions, which are suitable for mitigating slagging in accordance with the present invention are those wherein the metal is selected from zirconium; the alkaline earth metals, such as calcium, magnesium, barium, and strontium; and the rare earths, also known as elements of the lanthanide series, preferably La and Ce. Preferred are the alkaline earth metals, especially the oxides, and more preferred are such naturally occurring compositions as limestone. It is critical that alkali metals be substantially absent, however. Although the addition of an alkali metal compound to a coking process is beneficial for reducing the sulfur content of the coke, it is unsuitable for use in the instantly claimed invention because it aggravates slag formation in coking. It is known that alkali metals such as sodium react readily with vanadium, which is the major constituent in slag, to form sodium metavanadate or pyrovanadate (melting Point: 630.degree.-650.degree. C., p. B-134, 69th edition, Handbook of Chemistry and Physics). Compounds such as sodium metavanadate or pyrovanadate are highly undesirable because of their low melting points. They would eventually plate out and plug the gasifier. Alkaline-earth metals, rare earths, or zirconium react with vanadium to form high melting point solids. Thus, alkali metal is in fact to be avoided if slag formation is to be minimized, whereas alkaline-earth metals, rare earths, or zirconium are needed for slag reduction.

The inorganic metal composition can be introduced into the gasifier in several ways. For example, it can be added as fines and blown in with air through a separate line 62 at the bottom of the gasifier. It can also be introduced via line 64 at the bottom of the gasifier with the steam and oxygen-containing gas via line 56. It can also be introduced via line 66 into line 44 where it is mixed with the portion of heater coke passing to the gasifier. Preferred is when it is introduced at the bottom of the gasifier. This technique has the advantage in that the inorganic metal composition, even when added intermittently, provides some scouring action which may physically reduce slag formation on the gasifier grid caps.

It is critical, in the instant invention, that the inorganic metal compositions of this invention not be fed into the coking zone. There, the additive would serve as a seed for coke particles. The coking zone is a highly reducing environment. In such an environment the inorganic metal compositions react readily with sulfur, thus greatly reducing the sulfur content of the coke produced. In the instant invention the alkaline earth metal, rare earth, and/or zirconium is added at the bottom of the gasifier, where it is highly oxidizing. It is only under the highly oxidizing environment at the bottom of the gasifier, alkaline earth metal, rare earth, and/or zirconium will react with vanadium and nickel to form highly stable compounds such as Mg.sub.3 V.sub.2 O.sub.8 and Ca.sub.3 V.sub.2 O.sub.8 (melting point: 2177.degree. and 2516.degree. F., respectively). The reactions between alkaline earth metal and vanadium and nickel do not occur in highly reducing environments.

The amount of inorganic metal composition used in the practice of the present invention will be such that the molar ratio of metal of the composition to vanadium in the feed will range from about 0.5 to 1 to about 10 to 1, preferably from about 10 to 1.

Having thus described the present invention, and a preferred and most preferred embodiment thereof, it is believed that the same will become even more apparent by reference to the following examples. It will be appreciated, however, that the examples are presented for illustrative purposes and should not be construed as limiting the invention.

EXAMPLE 1

A static bed test was performed by placing various amounts of inorganic metal compositions as indicated in Table I below, and 30 g of heater coke from a commercial integrated fluid coker/gasifier unit in a Coors (alumina) evaporating dish. The dish was then placed it in a 12 inch Lindberg muffle furnace. In another dish, only 30 g of heater coke was used for comparison purposes. The heater coke had the following properties:

______________________________________Surface Area, m.sup.2 /g 9.1Pore Volume, cc/g 0.009Density - App. Bulk, g/cc 0.82Attrition, Davison Index 1Ash, wt. % 3.16Sulfur, wt. % 2.25V, wt. % 1.49Na, wppm 637Ni, wppm 2988______________________________________

The samples were purged with air and the furnace was heated at a rate of 9.degree. F./minute to a final temperature of 1750.degree. F., which was held there for four hours to ensure complete combustion/gasification. Two types of materials were left in the dishes, a hard slag material and a soft non-slag material. The amounts of each are shown in Table I below. The soft non-slag material was powdery and was easily poured from the dish. The hard slag material strongly adhered to the dish. This hard material is representative of the slag material in commercial gasifiers.

TABLE I______________________________________ Hard Soft Additive Deposit Deposit Reduction inAdditive Type g. g. g. Hard Dep. g.______________________________________None 0.00 0.54 0.55 --BaO 5.64 0.07 8.22 87CaCO.sub.3 3.75 0.14 4.52 74CeO.sub.2 6.32 0.19 7.56 35LaNO.sub.3 7.53 0.10 4.34 81La.sub.2 O.sub.3 4.01 0.07 5.99 85MgO 1.50 0.09 2.74 83SrCO.sub.3 5.55 0.16 6.57 70Zr(NO.sub.3).sub.2 --3H.sub.2 O 9.89 0.37 6.52 31Dolomite 4.00 0.05 4.86 90Limestone 3.42 0.05 4.12 90______________________________________

The above table illustrates the effectiveness of the inorganic compositions of the present invention for controlling slag formation.

EXAMPLE 2

This example was conducted to show the effectiveness of a representative sampling of inorganic compositions of the present invention at various concentrations of CaCO.sub.3, MgO and limestone for controlling slagging. The procedure of Example 1 above was followed for various amounts of the selected inorganic compositions. The results of hard slag material formation versus amounts of the various inorganic metal compositions were plotted and are presented in FIGS. 2 and 3 hereof.

EXAMPLE 3

This example was run to test the effectiveness of the inorganic compositions of the present invention, as represented by limestone, for controlling slag formation under conditions which would be closer to commercial gasifier conditions, such as lower levels of limestone, as indicated in FIG. 4 hereof, and a fluid bed operation. The test unit was comprised of a gas/water(steam) feed section, a reactor section, and a product overhead section.

At the start of the run, 30 grams of coke (identical to that used in Example 1 hereof) was charged into the reactor which consisted of a fluid bed quartz/vycor reactor with a frit at the bottom to provide uniform gas distribution. The reactor was housed in a split shell furnace which was preheated to a temperature of 1750.degree. F. Water was pumped to a steam generator and mixed with air. The steam generator was operated at a temperature of 150.degree. F. At this operating temperature and assuming that air is saturated after passing through the steam generator, it can be estimated that the steam/water partial pressure in the air used to combust/gasify coke was about 20 wt. %. The air rate was controlled at 0.74 l/minute. With the 1 inch diameter reactor used, the superficial gas velocity in the reactor was about 0.3 feet/second, which was sufficient for fluidizing the coke in the 1 inch reactor with minimal mass transfer limitations. The gas was passed through a frit which fluidized the coke bed. The steam and air reactor with the coke and form a product gas composed primarily of H.sub.2, CO, CO.sub.2, CH.sub.4, H.sub.2 S, H.sub.2 O, and diluent N.sub.2. There is disengaging volume in the top section of the reactor to reduce fine carryover into the overhead system.

The overhead gas proceeds to a cooler to condense the excess water in the gas and then to a filter to remove fines. After 4-6 hours of operations, most of the coke is gasified. Slag fanned is quantified by weighing the reactor after the run and comparing it to the weight of the reactor prior to the run. The results were plotted and are illustrated in FIG. 4 hereof.

Claims

1. In a fluid coking-gasification process for converting heavy hydrocarbonaceous materials to lower boiling products, which process comprises:

(a) introducing a heavy hydrocarbonaceous chargestock into a coking zone comprised of a bed of fluidized solids maintained at fluid coking conditions, including a temperature from about 850.degree. to 1200.degree. F. and a total pressure of up to about 150 psig, to produce a vapor phase product including normally liquid hydrocarbons, and coke, the coke depositing on the fluidized solids;

(b) introducing a portion of said solids with coke deposited thereon into a heating zone comprised of a fluidized bed of solid particles and operated at a temperature greater than said coking zone; and

(c) recycling a portion of said heated solids from said heating zone to said coking zone;

(d) introducing a second portion of said heated solids from the heating zone to a gasification zone comprised of a fluidized bed of solid particles and maintained at a temperature greater than the heating zone; and

(e) reacting said second portion of heated solids in said gasification zone with steam and an oxygen-containing gas, the improvement consisting essentially of using as an additive an effective amount of an inorganic metal composition, which metal is selected from the alkaline-earth metals, the rare earths, and zirconium to prevent slagging in the gasifier, wherein the inorganic metal composition is introduced into the process by : (i) adding it directly into the gasification zone through the bottom of the gasifier; or (ii) mixing it with the portion of heated solids passing from the heating zone to the gasification zone.

2. The process of claim I wherein the amount of inorganic metal composition used is such that the molar ratio of metal of the inorganic metal composition to vanadium in the feed is from about 0.5 to 1 to 10 to 1.

3. The process of claim 2 wherein the molar ratio of metal of the inorganic metal composition to vanadium in the feed is from about 2 to 1 to about 5 to 1.

4. The process of claim 2 wherein the inorganic metal composition is introduced at the bottom of the gasifier.

5. The process of claim 2 wherein the metal of the inorganic metal composition is an alkaline-earth metal.

6. The process of claim 5 wherein the alkaline-earth metal is selected from Mg and Ca.

7. The process of claim 2 wherein the metal of the inorganic metal composition is a rare earth metal.

8. The process of claim 7 wherein the rare earth metal is selected from La and Ce.

9. The process of claim 2 wherein the metal of the inorganic metal composition is zirconium.

10. The process of claim 2 wherein the inorganic metal composition is limestone.

11. The process of claim 10 wherein the limestone is added at the bottom of the gasifier.

12. The process of claim 1 wherein the heating zone is operated at a temperature which is about 100.degree. to 400.degree. F. higher than that of the coking zone.

13. The process of claim 1 wherein the gasification zone is operated at a temperature from about 1600.degree. to 2000.degree. F.

14. The process of claim 2 wherein the heating zone is operated at a temperature which is about 100.degree. to 400.degree. F. higher than that of the coking zone and the gasification zone is operated at a temperature from about 1600.degree. to about 2000.degree. F.

15. The process of claim 14 wherein the metal of the inorganic metal composition is an alkaline-earth metal.