Process for degassing condensed sulfur from a Claus sulfur recovery system

Abstract

A process of producing degassed liquid sulfur using process gas containing H.sub.2S to agitate the liquid sulfur being degassed while in contact with a degassing catalyst. Process gas is less costly and less complicated and quickly accomplishes substantial degassing rendering the liquid sulfur much safer in storage and transportation.

Claims

1. A process for producing liquid sulfur that is degassed of H.sub.2S, wherein the process comprises: a) providing a sulfur degassing catalyst and liquid sulfur into a vessel wherein the sulfur degassing catalyst and liquid sulfur define a contact zone; b) directing condensed products from a Claus plant into the contact zone of the vessel wherein the condensed products include elemental sulfur, dissolved H.sub.2S and H.sub.2S.sub.x where x≧2; c) catalyzing the conversion of H.sub.2S.sub.x on the surface of the sulfur degassing catalyst to form H.sub.2S and elemental sulfur; d) directing a process gas from the Claus plant and increasing the pressure of the process gas and directing the elevated pressure process gas into the contact zone of the vessel to agitate the sulfur degassing catalyst and liquid sulfur and carry H.sub.2S that has formed on the surface of the sulfur degassing catalyst away from the sulfur degassing catalyst; wherein the process gas includes H.sub.2S; e) exhausting the processes gases along with H.sub.2S from the contact zone back to the Claus plant for further processing in the Claus plant; and f) extracting liquid sulfur that is degassed of H.sub.2S from the contact zone.

2. The process according to claim 1, wherein the step of providing a sulfur degassing catalyst comprises providing a plurality of high surface area alumina particles constrained to prevent being removed or carried away from the contact zone.

3. The process according to claim 2, wherein the step of providing a sulfur degassing catalyst further comprises providing a plurality of high surface area alumina particles impregnated with iron oxide.

4. The process according to claim 1, wherein the step of providing a sulfur degassing catalyst comprises providing one or more low surface area alumina porous ceramic foam supports coated with high surface alumina particles.

5. The process according to claim 4, wherein the step of providing a sulfur degassing catalyst further comprises providing one or more low surface area alumina porous ceramic foam supports coated with high surface alumina particles that is impregnated with iron oxide.

6. The process according to claim 1, wherein the process gas directed into the contact zone includes at least 0.5% H.sub.2S by volume.

7. The process according to claim 1 further including a step of blending process gas drawn from an intermediate step of the Claus plant with the elevated pressure process gas prior to being directed into the contact zone.

8. The process according to claim 1, the Claus process includes at least three condensers, but only the liquid sulfur from the first two condensers is subject to degassing in the contact zone.

9. The process according to claim 1 further including converting H.sub.2S to elemental sulfur by reacting on the surface of the catalyst with SO.sub.2 in the process gas by the following reaction: 2H.sub.2S+SO.sub.23/xS.sub.x+2H.sub.2O.

10. A process for producing liquid sulfur that is degassed of H.sub.2S, wherein the process comprises: a) providing a Claus plant for desulfurizing H.sub.2S containing gases, wherein the Claus plant includes a number of components including a burner for converting some H.sub.2S to SO.sub.2 along with elevated pressure process gas, a reaction furnace for converting at least some H.sub.2S and SO.sub.2 to elemental sulfur, a first condenser for condensing the sulfur from the process gas exiting the reaction furnace, at least one additional catalytic reactor for converting a portion of the H.sub.2S in the process gas from the first condenser to elemental sulfur, a second condenser for condensing the sulfur in the gases exiting the one additional catalytic reactor; b) providing a sulfur degassing catalyst and liquid sulfur into a vessel wherein the sulfur degassing catalyst and liquid sulfur define a contact zone; c) directing condensed products from at least one condenser of the Claus plant to the vessel, wherein the condensed products include elemental sulfur, dissolved H.sub.2S and H.sub.2S.sub.x where x≧2; d) catalyzing the conversion of H.sub.2S.sub.x on the surface of the sulfur degassing catalyst in the contact zone to form H.sub.2S and elemental sulfur; e) directing process gas from the Claus plant and increasing the pressure of the process gas and directing the elevated pressure process gas into the contact zone of the vessel to agitate the sulfur degassing catalyst and liquid sulfur and carry H.sub.2S that has formed on the surface of the sulfur degassing catalyst away from the sulfur degassing catalyst; wherein the process gas includes H.sub.2S; f) exhausting the processes gas along with H.sub.2S from the contact zone back to the Claus plant for further processing in the Claus plant; and g) extracting liquid sulfur that is degassed of H.sub.2S from the contact zone.

11. The process according to claim 10, wherein the step of providing a sulfur degassing catalyst comprises providing a plurality of high surface area alumina particles constrained to prevent being removed or carried away from the contact zone.

12. The process according to claim 11, wherein the step of providing a sulfur degassing catalyst further comprises providing a plurality of high surface area alumina particles impregnated with iron oxide.

13. The process according to claim 10, wherein the step of providing a sulfur degassing catalyst comprises providing one or more low surface area alumina porous ceramic foam supports coated with high surface alumina particles.

14. The process according to claim 13, wherein the step of providing a sulfur degassing catalyst further comprises providing one or more low surface area alumina porous ceramic foam supports coated with high surface alumina particles that is impregnated with iron oxide.

15. The process according to claim 10, wherein the process gas directed into the contact zone includes at least 0.5% H.sub.2S by volume.

16. The process according to claim 10 further including a step of blending process gas drawn from an intermediate step of the Claus plant with the elevated pressure process gas prior to being directed into the contact zone.

17. The process according to claim 10, the Claus process includes at least three condensers, but only the liquid sulfur from the first two condensers is subjected to degassing in the contact zone.

18. The process according to claim 10 further including converting H.sub.2S to elemental sulfur by reacting on the surface of the catalyst with SO.sub.2 in the process gas by the following reaction: 2H.sub.2S+SO.sub.23/x S.sub.x+2H.sub.2O.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A more complete understanding of the present invention and benefits thereof may be acquired by referring to the follow description taken in conjunction with the accompanying drawings in which:

(2) FIG. 1 is a flow diagram showing a basic and conventional Claus sulfur recovery system;

(3) FIG. 2 is a flow diagram showing liquid sulfur being degassed of H.sub.2S;

(4) FIG. 3 is a flow diagram of the vessel connected to the Claus process; and

(5) FIG. 4 is a flow diagram of an alternative embodiment showing the liquid sulfur being degassed of H.sub.2S.

DETAILED DESCRIPTION

(6) Turning now to the detailed description of the preferred arrangement or arrangements of the present invention, it should be understood that the inventive features and concepts may be manifested in other arrangements and that the scope of the invention is not limited to the embodiments described or illustrated. The scope of the invention is intended only to be limited by the scope of the claims that follow.

(7) Referring now to FIG. 1, a line diagram for a conventional Claus Sulfur Recovery Plant is generally indicated by the numeral 10. Claus Plants have been in use for more than a century at petroleum refineries to remove sulfur from gases containing H.sub.2S. Undertaking a brief explanation of a conventional Claus Plant, referring to Claus Sulfur Recovery Plant 10, gas having sulfur, typically in the form of H.sub.2S, enters via conduit 12. A burner 15 along with reaction furnace 18 are provided to burn and oxidize at least part of the H.sub.2S to elemental sulfur SO.sub.2 and water wherein the reaction is:
10H.sub.2S+5O2.fwdarw.2H.sub.2S+SO.sub.2+7/2S.sub.2+8H.sub.2O.

(8) These very hot gases and vapors are cooled down in a waste heat boiler 19 and a first condenser 22 where the elemental sulfur is condensed and removed at liquid discharge conduit 25. Cooling water is provided to both the waste heat boiler 19 and to the condenser 22, as shown at inlet 23 to make steam, as shown at outlet 24, for use in making electricity or elsewhere in the in the Claus Sulfur Recovery Plant 10 or in the larger industrial plant that is not shown. The remaining gases from the first condenser 22 are directed through the gas conduit 28 to reheater 30 where the gases are reheated and then delivered to a catalytic conversion to elemental sulfur for converting remaining H.sub.2S and SO.sub.2 to elemental sulfur. The chemical process is generally described as follows:
2H.sub.2S+SO.sub.2.fwdarw.3S+2H.sub.2O.

(9) Again, the process gases are cooled in the second sulfur condenser 32 so that elemental sulfur may be condensed to a liquid and removed at the second liquid discharge conduit 35. The gases are conventionally directed by a conduit 38 to further sulfur recovery steps including catalytic reactor 41 and 51 to recover liquid sulfur at discharge conduits 45 and 55.

(10) It should be noted that more thorough descriptions of a Claus system may be found in many other places and there are doubtless variations known in the art. This description has been presented simply to describe the improvement related to degassing the liquid sulfur acquired by most any Claus system.

(11) Referring now to FIG. 2, a sulfur degassing vessel 60 is arranged to receive the liquid sulfur from liquid discharge conduits 25 and 35 at a lower portion of the vessel 60 or at the bottom of the vessel 60. Inside the vessel 60 is liquid sulfur with a contained catalyst 62 held within a contact zone 65 that is generally above the lower portion of the vessel 60. A degassed liquid sulfur discharge line 66 is arrange to remove liquid sulfur above the contact zone such that liquid sulfur entering the vessel 60 must pass completely through the contact zone 65 or at least through a substantial portion of the contact zone 65. The catalyst 62 may take one of several forms. The first form is a plurality of high surface area alumina particles (spheres, extrudates, etc.) constrained to prevent being removed or carried away by sulfur flow from the vessel 60. A second form is a plurality of similarly constrained high surface area alumina particles impregnated with iron oxides. A third form is one or more low surface area alumina porous ceramic foam supports coated with high surface alumina particles with or without impregnated iron oxide.

(12) The catalyst 62 converts H.sub.2S.sub.x to H.sub.2S and elemental sulfur. Reducing the content of H.sub.2S.sub.x at this stage of the production of liquid sulfur has been found to substantially reduce the tendency of stored liquid sulfur to slowly yield H.sub.2S gas. The productivity of the catalyst 62 is enhanced by agitation, especially by gas. In the present invention, the gas used to stir the liquid in the contact zone 65 is process gas from the tail of the Claus process delivered through conduit 58A of H.sub.2S containing tail gas. The H.sub.2S containing tail gas is taken from conduit 58 at the tail end of the plant and pressurized via a compressor or steam powered ejector 58B up to a suitable pressure for the system 10 at the sulfur degassing vessel 60. Gas for agitation may be augmented by process gas from either gas conduit 28 or gas conduit 38 or both via lines 28A and 28B Metering valves may be arranged in lines 28A and 28B to control the amount of process gas that may be injected into line 58A and fed to the bottom of the vessel in a sparger 63 to agitate the liquid and the catalyst 62 to carry produced H.sub.2S back to the Claus Sulfur Recovery Plant 10.

(13) Once the gas has passed through the vessel 60, it exits at exit conduit 68 and rejoins the Claus process downstream of the source of the process gas at conduit 28. In the preferred arrangement, the process gas rejoins the Claus process at conduit 48 via conduit 48A. It should be noted that the process gas may optionally be arranged to rejoin the Claus process at conduit 38 as shown by dotted line 38A. However, there is a more significant pressure drop between conduits 28 and 48 to allow for more vigorous stirring of the catalyst 62 by the process gas from sparger 63. For even more vigorous stirring, the process gas may optionally be arranged to rejoin the Claus process further along the system such as at conduit 51A. This arrangement is shown by dotted line 48B and may be preferred if the source of the process gas used in vessel 60 comes from conduit 38 via conduit 28B. While the process gas from the vessel 60 will not have been subjected to all of the successive treatments in the catalytic reactors 31, 41 and 51, it may have some vaporous elemental sulfur that could be condensed in condenser 52 and may be subjected to further sulfur removal treatment in a tail gas unit, which are conventional in Claus plants.

(14) One additional side reaction occurring in the contact zone 65 worth mentioning is additional conversion of H.sub.2S to elemental sulfur. The process gas includes some SO.sub.2 and may react on the surface of the catalyst with H.sub.2S that may be condensed in the liquid sulfur, emanating from the liquid sulfur by the decomposition of H.sub.2S.sub.x, or contained in the process gas. This reaction is the same chemical reaction occurring in the Claus process and is generally described as: 2H.sub.2S+SO.sub.23/x S.sub.x+2 H.sub.2O. Having additional active catalyst for this chemical reaction to occur yields more liquid sulfur separated from the industrial process and less sulfur compounds in process gas.

(15) It is noted that it has long been recognized that the catalytic process occurring in contact zone 65 is an equilibrium reaction and therefore, gases that have been used for agitating the catalyst always exclude H.sub.2S. This is more expensive than simply using process gas from the tail of the Claus plant. And, the process gas includes enough H.sub.2S to warrant further sulfur recovery steps so that H.sub.2S recovered in the vessel 60 is simply and efficiently disposed. As compared to an arrangement using air or nitrogen, the air and nitrogen will have acquired small amounts of H.sub.2S and elemental sulfur vapor that must be handled. These gases usually must be directed to a part of the sulfur recovery unit where combustion can convert the elemental sulfur to SO.sub.2 to avoid plugging the vent line from the process either contributing additional SO.sub.2 emissions or requiring recycling with some motive fluid such as air or steam. This adds additional costs to operating a Claus process.

(16) The process gas, as noted above generally includes H.sub.2S. Process gases in line 28 may contain about 4% to about 9% by volume H.sub.2S and typically about 8% by volume H.sub.2S. Process gases in line 38 typically comprise less H.sub.2S, but certainly have sufficient pressure to agitate the catalyst 62 and return to the Claus process 10. Process gases in line 38 may have between 2% to 5% H.sub.2S by volume and typically about 4% by volume H.sub.2S. Process gases in line 48 still retain sufficient pressure to be used to agitate the catalyst 62 and has a lower H.sub.2S content being about 0.5% H.sub.2S to about 3% H.sub.2S by volume and typically about 1% H.sub.2S to about 2% H.sub.2S by volume.

(17) The full Claus process with the vessel 60 is generally shown in FIG. 3 showing the side stream of process gas being taken from line 28 and being carried through the vessel 60 and back into the Claus process at line 38.

(18) The vessel 60 may optionally be arranged to receive liquid sulfur discharged through drains 45 and 55 for degassing. In the preferred arrangement, the liquid sulfur discharge lines 45 and 55 are combined with the degassed liquid sulfur in line 66. It has been found that such small streams of liquid sulfur really do not contain much H.sub.2S.sub.x that needs degassing. Most of the liquid sulfur is gathered from the first two condensers 22 and 32.

(19) In an alternative embodiment shown in FIG. 4, the liquid sulfur may be received at the top of the vessel 60 and liquid elemental sulfur having the sulfanes removed may be withdrawn at the bottom of the vessel 60. In this embodiment, the sulfur is travelling counter to the flow of the process gas through the reaction zone 65. In FIG. 2, the catalyst zone 65 is shown as being liquid continuous, whereas, in the alternative embodiment shown in FIG. 4, the catalyst zone may be gas continuous with the liquid sulfur trickling down through the contact zone 65.

(20) Although the systems and processes described herein have been described in detail, it should be understood that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the invention as defined by the following claims. Those skilled in the art may be able to study the preferred embodiments and identify other ways to practice the invention that are not exactly as described herein. It is the intent of the inventors that variations and equivalents of the invention are within the scope of the claims while the description, abstract and drawings are not to be used to limit the scope of the invention. The invention is specifically intended to be as broad as the claims below and their equivalents.