WO2017120302A1

WO2017120302A1 - Claus process for sulfur recovery with intermediate water vapor removal by adsorption

Info

Publication number: WO2017120302A1
Application number: PCT/US2017/012287
Authority: WO
Inventors: Cemal Ercan; Rashid A. OTHMAN; Yuguo Wang
Original assignee: Saudi Arabian Oil Co; Aramco Services Co
Current assignee: Saudi Arabian Oil Co; Aramco Services Co
Priority date: 2016-01-05
Filing date: 2017-01-05
Publication date: 2017-07-13
Anticipated expiration: 2018-07-05
Also published as: US10005666B2; US9701537B1; US20170190574A1; US20170260049A1

Abstract

A method for recovering sulfur is disclosed, comprising the steps of feeding an acid gas stream to a combustion furnace, condensing the cooled furnace stream to produce a first gas stream, feeding the first gas stream to a first adsorber comprises a molecular sieve, feeding the first hot dry gas stream to a first catalytic reactor, cooling the first catalytic outlet stream in a first condenser, feeding the second gas stream to a second adsorber, feeding the second hot dry gas stream to a second catalytic reactor, cooling the second catalytic outlet stream in a second condenser, introducing the third gas stream to a third adsorber, feeding the third hot dry gas stream to a third catalytic reactor to produce a third catalytic outlet stream, and cooling the third catalytic outlet stream in a third condenser to produce a third sulfur stream and a tail gas stream.

Description

PCT PATINT APPLICATION

CLAUS PROCESS FOR SULFUR RECOVERY WITH INTERMEDIATE WATER VAPOR REMOVAL BY ADSORPTION

TECHNICAL FIELP [0001] Disclosed are rnsthods for sulfer recovery,

BACKGROUND

[£fO02J Sulfur recovery refers to the con version of hydrogen sulfide (HiS) to elemental sulfur, H dr gen sulfide_, is s byproduct of processing natural gas and refm¾¾ ¼gh-s¾lfiir crude oils. The- coriventionalmethcd of sulfer recovery' is the Clao-s process. Approximatel 90 percent to 95 percent . {%) of recovered sulfur I produced by the Clays process. A conventional CJaus process can recover between 95 % arid 98 % of the hydrogen sulfide.

$Q0¾ The conventional Claris process includes a thermal combustion stage: and a eataiytie reaction stage. In terms of equipment, the Claus plant (Claus unit) includes a thermal reactor and two or three catalytic reactors (Claus converters), Typical sulfur recovery ^' efficiencies for Claus plants with two Claus converters (reactors) is bet een 90 and 97%, and for a Cl $ plant with three converters between 95 and 98%. But there is increasing demand to achieve higher sulfur removal and recover}' efficiency due to. tight emissions ^' regulations.- Recent, environmental re le ions regarding sulfur oxides (SQx) emissions place a stringent requirement on commercial sulfur recovery and accordingly* -most countries require sulfur recovery efficiency in the range of 98.5% to 99.9% or higher.

|0O84 The addition of a aii-gas treatment unit (TCTFU) ca increase sulfur recovery to or above 99.9%. but requires complex and expensive equiproent The TGTU entails either an add-on unit at the end of the Claus unit or a modification to the Claus unit itself. The add-on TGTli at the en of the Claas unit is generally -used when the Glaus process includes two Ciaus .converters. Although there are_: several varieties of fail gas treatment^■technologies, they can ..be grouped into the ib!!owing: four broad categories: sub-dew point Claus process, direct oxidation of ¾S to sulfur, salfiif dioxide ($<¼) redaction and recovery of ¾$, and S¾S combustion to SO_?, and recovery of SC¾. OOOSj Sub-dew point Clans .processes are processes based on a Glaus converter performing at temperatures below the sulfur dew point (lower temperature is desirable due to equilibrium nature of the Claus catalytic reaction). Sub-dew point processes provide high equilibrium conversions in one catalyst bed, but are complicated by the need for periodic catalyst regeneration by sulfur evaporation at. elevated temperatures, To accommodate for regeneration, such processes are usually performed in two or three (or even more) parallel reactors, periodically undergoing reaction, and regeneration.; Cold-bed-adsorption (CBA) is, the most efficient sub-dew point process and can achieve 99% sulfur recovery.: MKiJ Processes involving direct; oxidation of ¾S to sulfur are based on selective oxidation of I¾S by oxygen to elemental sulfur using selective catalysts.

{&0Θ7} TGTO technology based on S(¾. reductio and. recovery of ¾$ involves the; catalytic hydrogenation of leftover sulfur species to ¾S_t absorption of the ¾S with amine solution and then recycling the ¾S back to the Clays furnace.

I^'GTU^" technolog based on ¾S combustion to S<¾ and: recovery of SO? involves the combustion of leftover H₂S i n th e tail gas stream to 50_¾ absorption of S¾ with a solvent (wet scrubbing), and recycling the $(¾ back to the feed to Glaus plant. Although ^'S<¾ scrubbing, also known as flue gas scrubbing, has not been commercially tested as a TG U, the technology has been extensively used as flue: gas scrubbing for coal based, power stations.

SUMMARY. OF Till INVENTION

[0 9) Disclosed are methods for sulfur recovery, 08IO in -a first s ect,: a method ^'to recover si ¾r irom hydrogen sulfide in an acid gas stream is provided, The method includes the steps of feeding the acid gas stream to a combustion furnace to produce a furnace outlet stream. The combustion furnace configured to convert the hydrogen sulfide to elemental sulfur, where the furnace outlet stream inclu es elemental sulfur, hydrogen sulfide, .sulfur dioxide, and water vapor. The step of aittodueirig^' the furnace outlet stream, to a waste heat boiler to produce a cooled furnace outlet stream, the waste heat boiler configured to reduce a temperature of the furnace outlet .stream, condensing the cooled feraaee stream in. a sulfur condenser to produce a liquid sulfur stream and a first gas stream, the sulfur condenser configured to reduce a temperature of the cooled furnace strea , to a temperature below a dew point of elemental sulfur and above a dew point of water, feeding: the first: gas stream: to a first adsorber to produce a first dry gas stream and a first: water stream, wherein the first: adso ber Includes s molecular sieve, wherein the first dry gas stream is in the . absence of water vapor, wherein the first dry gas stream includes hydrogen sulfide and sulfur dioxide. The method further including the steps of heating the first dry gas stream in a. first reheater to produce a first hot dty gas stream, whercfcr the first hot dry gas stream is at a first temperature, feeding the first hot dry gas stream to a first catalytic reactor to produce a first catalytic outlet stream, wherein the -firs catalytic outle stream includes elemental sulfur, hydrogen, sulfide, sulfur dioxide, and water vapor, cooling the first catalytic outlet stream in a. first condenser to produce a . first sulfur stream, and second gas stream, the first eondefiser configured to condense the elemental sulfur in the first catalytic outle stream such that_, the first sulfur stream includes. liquid sulfur, wherein a temperature in the first, condenser is etween the dew point of sulfur and the dew point of water, wherein the second gas stream includes hydrogen sulfide, sulfur dioxide, and water vapor, feeding the second gas stream to a second adsorber to produce a second dry gas: stream and a second water stream, wherein the second adsorber includes a molecular sieve, wherein the second dry gas stream includes, hydrogen sulfide and sulfur dioxide, wherein the Second dry gas stream is in the absence of water vapor, heating the second dry gas stream, in secon reheater to produc a second hot dry. gas stream. The second hot dry gas stream is at a second temperature, where the second temperature is lower than the first temperature,: The method further includes the steps of feeding the second hot dry gas stream to a second catalytic reactor to produce a second catalytic outlet stream, wherein the second catalytic outlet stream includes elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor, cooling the second catalytic outlet stream in a second condenser to produce a second sulfur stream and a third gas stream, the second condenser configured to condense the elemental sulfur in the second catalytic outlet stream suc that the second sulfur stream includes liquid sulfur, wherein a temperature in the second condenser is between the dew point of sulfur and the dew point of water, wherein t e third gas stream includes hydrogen sulfid , sulfur dioxide, and water vapor, introducing the third gas stream to a third adsorber to produce a third dry gas stream and a third water stream, wherein the third adsorber includes a -molecular sieve, wherein the third dry gas stream includes hydrogen sulfide and sulfur dioxide, wherein the third dry gas stream is-ifl the absence of water vapor.., heating the third dry gas stream in third reheater to produce a third hot dry gas stream. The third, hot dry gas stream is at a third, temperature, where the third temperature is lower than th -second temperature., The. method ^■further including the steps of feeding the third hot dry gas stream-to a third catalytic reactor to produce a third catalytic outlet stream, wherein the third catalytic outlet^■..stream includes elemental sulfur, hydrogen sulfide, sulfur dioxide, and wafer vapor, and cooling the third catalytic, outiet; stream, in a third condenser to produce a third sulfur stream and, a tail gas stream, the third condenser configured to condense the elemental sulfur ^: in the third catalytic outiet stream such that the third sulfur s ream includes liquid sulfur, wherein a tem erature in. the third condenser is between the dew point of sulfur arid the dew point of water, wherein the tail gas stream includ.es hydrogen. Sulfide,- sulfur dioxide, and water vapor. OM} its certain aspects of the present invention, a- total conversion can be determined. In certain aspects of the present invention, the total conversion exceeds 99 % by weight In .certain ^' spects of the present invention, the m lecular sieve is molecular sieve 3 A, In certain aspects of the present invention, the first temperature is 235 °C. In certain- aspects of the present invention, the second temperature: is 215 in certain aspects of ^'the¹ present invention, the third temperature is 2.05 *C. O0i2J in a second aspect of the present invention, a system to recover sulfur from hydrogen sulfide fa an. acid gas stream is provided. The system includes a combustion furnace, the combustion fttraace configured to convert the hydrogen sulfide to elemental sulfur to produce a furnace outlet ^'stream,, wherein the furnace outlet ste m includes elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor, a waste heat boiler flu idly connected to the combustion furnace, the waste heat boiler configured to remove heat from the furnace outlet stream to produce a cooled furnace stream, a sulfur condenser fluidly connected to the waste . heat boiler, the sulfur condenser configured to condense the elemental ^•Sulfur in: coaled furnace stream to produce a li uid sulfur stream arid, a first gas stream, wherein l te gas stream is in the absence of elemental sulfur, wherein the first gas stream includes water vapor... a first adsorber fluidly connected to the sulfur -condenser, the first adsorber configured to remove water vapor from the first gas stream to produce a first dry gas stream and a first water stream, wherein the first adsorber includes a molecular sieve, wherein the first dry gas stream includes hydrogen sulfide and sulfur dioxide and is in the absence of water vapor,, a first Claus catalytic- stage fluidly connected to the first adsorber, the first Claus catalytic stage configured to produce a first sulfur stream and a second gas stream, a second adsorber fluidly .connected io" the -first Claws catalytic stage, the second adsorber configured to remove water vapor from the second gas to produce a second dry gas stream, wherein the second adsorber includes a molecular sieve, wherein the secon dry gas stream includes hydrogen sulfide and. sulfur dioxide and is in the absence of water vapor, a, second Cl ws catalytic stage flindly connected to the second adsorber, t e second Claus catalytic stage- configured to produce a secottd sai&r streara and a third, gas stream, a third adsorber fluidly connected to the second Claus catalytic stage, the third adsorber configured to remove water vapor from the third gas to produce a third dry gas stream, wherein the third adsorber includes a molecular sieve, wherein the third dry gas stream includes hydrogen sulfide and sulfur dioxide and is i the absence of water vapor, and a third Claus catalytic stage fluidly connected to the third adsorber, the third Claus catalytic stage configured t produce a third sulfur stream and a tail gas stream. f0Qi3] In -certain, aspects of the present ^'.invention, a total conversion can be determined, in certain aspects .of the present invention, the total -conversion exceeds 99. % by weight In certain aspect o -the present invention, the molecular sieve is molecular sieve 3A. in certain -aspects of the present invention, the first Claus catalytic stage includes a first re-heater fluidly connected to the first adsorber, the first reheater eon -figured.: to ^' _.increase a temperature of the first dr gas stream to produce a first hot dr gas stream:, wherein the first hot dry gas stream is ¾t a first temperature, a first ^'catalytic reactor 0» idly connected to the first .reheaier, the first- catalytic reactor Configured to convert hydrogen sulfide and sulfur dioxide to elemental sulfur to produce- a first catalytic- outlet stream, wherein the first: catalytic -outlet stream includes hydrogen sulfide, sulfur dioxide, elemental sulfur and water, and a first condenser the first condenser fluidly connected to the first catalytic reactor, the first condenser configured to condense the elemental sulfur in the first catalytic outlet stream to- produce a first sulfur stream and the second: gas . stream, wherein the second gas stream inclu es hydrogen sulfide, sulfur dioxide, and water vapor, m certain aspects of the present invention* the first temperature is 233 " I.. In certain aspects of the presen mventio¾ the second Ciaus catalytic Stage inclades a second reheater flnidly connected to the second adsorber, the second reheater configured to increase a temperature of the second dry gas s tream to produce a second hot dry gas stream, wherei the second hot dry gas stream is at a second temperature, a second catalytic reactor fluidly connected to the second reheater, the second catalytic reactor configured to convert hydrogen, sulfide and ^"■■sulfur dioxide -to. elemental -sulfur to produce a second catalytic outlet stream, wherein the second catalytic outlet stream includes hydrogen sulfide. $ulfur dioxide, -elemental sulfur and water, and a .second condenser, the second condenser fluidly connected to the second catalytic reactor, the second condenser configured o condense the elemental sjui&f hi the second catalytic outlet stream to produce a second sulfur stream, and the second gas stream, wherein the second gas stream^' includes hydrogen sulfide, sulfur dioxide, sod water vapor.: In certain aspects of the present invention, the second temperature is 215 °C. In certain aspects of the present invention, the third Claus catalytic stage includes a third: reheater fluidly connected to the third adsorber, the third reheater configured to increase a temperature of the third dry gas stream to produce a third hot dry gas stream, Wherein, the third: ho dry gas stream is at a third temperature, a third catalytic reactor fluidly connected to the third reheater, the third catalytic reactor configured to convert hydrogen sulfide and sulfur dioxide to elemental sulffcr to produce a third catalytic outlet stream, wherein the third catalytic outlet stream includes hydrogen sulfide, sulfur dioxide, elemental sulfur and water, and a third condenser, the third condenser fluidly connected to the third catalytic reactor, the third condense configured to condense the elemental sulfur hi the third catalytic outlet stream to produce a third sulfur stream and the third gas stream, wherein the third gas stream includes hydrogen sulfide, sulfur dioxide, and water vapor. In certain aspects of the present invention, the third temperature is 205 °C. BRIEF DESCRIPTIO O DRA I GS

[0014] These and other features_* aspects, and advantages of the inventive scope will become better understood with regard to the following descriptions, claims, an accompanying drawings, it is to- be noted, however, that the drawings illustrate Only several embodiments and are therefore not o be. considered limiting of the invention's scope.

[0915] F G. 1 is a process flow diagram of the process of the present invention including three adsorbers, 90.16] FIG. 2 is, a process flow diagram of a conventional C!aus process having two catalytic reactors.

[0017] FIG, 3 is a process flow diagram of a conventional Glaus process haying- three catalytic reactors,

[8038] FIG. 4. ?S; a process flow diagram of the process .of/the present invention including one adsorber.

[0019] FIG, 5 is a process flow diagram of the process of the present in vention includin two adsorbers.

(9020] FIG, 6 is a process flow diagram of the process of the present invention me lading one adsorber,

[0021 J FIG. 7 is: a process flow diagram of the process of the presen invention including one adsorber,

[9022] FIG . 8 is a proces flow diagram of the process of the present invention . inc luding two adsorber,

[9023] FIG. 9 is a process flow diagram of the: process of e present invention including one adsorbers. j 024] FIG; 10 is a process flo diagram of an adsorber,

^■[0025] FIG, 1 1 is a depiction; of the isotherms for water vapor on molecular sieve 3A. DETAILED DESCRIPTIO OF THE . INVE TION

[00 61 While the inventive scope will, be described with several embodiments, it is understood, tha one of ordinary skill in; ike relevant art will appreciate that many examples, variations^'- mi&al-emtloas to the apparatus and merhods described herein are within the scope and spirit of the invention. Accordingly, the embodiments described are set forth without any loss of generality, and without imposin limitations, on the eiaiiri Invention, Those of skill in the art understand that the inventive scope includes a!l possible- combinations and uses of particular features described i the specification-

{ (27J The present invention provides a method tor recovering elemental sulfur from an acid gas stream containing hydrogen sulfide. The method is an improvement to the conventional C!aus process. The method of the present invention .advantageously Increases the amount of elemental .sulfur recovered and therefore: reduces the amount of sulfur dioxide vented to atmosphere over a conventional ^'Claus process. Thus, the present invention enables a Glaus process to meet .more. -stringent, sulfur regulations.

| S2#] As used herein, arid unless otherwise specified the term "elemental sulfur" refers: to sulfu vapor, which can be present as S_¾ ,S¾ $4, S$, S& S_?. and ¾, due to simple polymerization. Without being bound to a particular theory,, it is noted that high reaction temperatures favor the production of S3 and lower reaction temperatures favor formation of ¾.

(0029] As used herein, "dew point" refers to the temperature of saturation of a vapor with a liquid. St is the temperature a which ^'liquid evaporates at the same rate at which i condenses. Dew point for any .compound is a function of the pressure and the composition of the vapor, including f action of compound in the apor. Below the dew point of a_. component, the componen will condense from the vapor phase,

|0Ο3β| The method o the present invention i ncorporates remo val of wate vapor ¾0) to drive the Glaus catalytic reaction toward conversion to elemental sulfur. The Claus catalytic reaction occurs in the catalytic reactors of the Claus process, according to the following equation:

|0 32] where, Ss is a form of elemental sulfur and AH is- the change in enthalpy and the negative vafee indicates thai the reaction is exothermic. -Reaction 0}» the Claus catalytic reaction, Is a reversible exothermic reaction, Tfee extent of reactio is imited by the equilibrium-value; One .way to drive the reaction toward the right is to lower the temper tuni. However, the ability to reduce the temperature is limited by the sulfur dew point. Temperatures below the sulfur dew point leads to sulfu condensation in the catalyst bed of the catalytic reactor. Sulfur .condensation can lead: to impairment of the catalyst surface and to catalys deactivation.- As a result, the temperature in the catalytic reactors is maintained at a temperature between 5 °C and 10 ^QC, above the sulfur: dew poin Sulfur condenses at temperatures at or below 175 ^eC, alternately -at temperatures between 175 °G - 200 °C, and alternately at temperatures at or below 200 *C. Conventional Claus units are designed such that the lowest reaction, temperature is. only reached in the last catalytic reactor in the catalytic, reaction stage. IK⁾33| Another way to increase conversion to elemental, sulfur in: reaction (1) is to remove reaction pmdiscts >m the reaction medium, The- .removal, .of -.reaction .products results in a higher conversion in atv equilibrium, reaction. The onventional Claus process focuses on the removal of sulfur by performing reaction (I) ..in a series of two or three catalytic reactors that include intermediate removal of sulfur in condensers. The present invention advantageously incorporates die .additional step of selective removal of water between catalytic reactors to improve the equilibrium in the Clans catalytic reaction. The selective removal of wate can shift reaction (1) ^'further to the right due to the second order dependenc of the equilibrium constant on water vapor partial pressure: as shown in the following equation:

) \ where, P¾₀ is the partial pressure of water, P_$s is the partial pressure of sulfur, the partial pressure of hydrogen sulfide and ¾¾¾ is he partial pressure of sulfur dioxide and Keq is the equilibrium constant. Reaction (2) has a water vapor partial -pressure dependency of power to 2, while a sulfur -partial pressure dependency of power to 3/8. Without being bound by a particular theory, it, is understood that eqniiibrtttm constant, K_ei is function of temperature, such that at a given temperature, the value of K« is fixed. When equilibriu is disturbed, for example by removing either product or reactants, the reaction will shift to counterbalance the disturbance {that is to re-establish- the equilibrium). [0036] ^'TSie method of the present invention incorporates the removal of water vapor" in the : catalytic reaction stage of the Claus process. The- njethod for recovering su liar includes an absorber. laced u stream from one or sn re of the catalytic reactors of the Clans unit,

|0037] An acid gas stream and an air feed are fed to & combustion: furnace (the Claus thermal stage), where hydrogen sulfide, sulfur dioxide, and oxygen form elemental, sulfur- accordin to the Clau thermal reactions, shown in the following equations:

3¾ ZH S6* M»0,} .&%^'-■ 56™

(4) 0640) Reaction (3), a combustion reaction is exothermi indicated by the negative AH. Reaction (4), the thermal Glaus reaction, is a reversible, eiidothermie reaction,, indieated, by the positive ΔΜ The S% ears be from any source capable of providing S<¾ to fee . consumed in reaction (4). Examples of sources of SC¾ include feeing prodisced in reaction (3), being a component of the acid gas stream, being present as a result of a separate feed t the cotn iistion &rnace that eonta ns Oj, and a combination of the same,

[804!) The acid gas: stream ca be from any source that produces stream containing hydrogen sulfide (¾S). The acid gas stream can include ¾S, carbon dioxide (CO?), other gases, and combinations of the same, The other gases can include carbo -monoxide {CO), water (¾0^'), nitrogen ( ½), hydrogen (¾), and combinations of the same. The nature and composition of the acid gas stream depends on the process that is the source- for the ael gas stream and can be determined using any technology capable of analyzing the composition of an acid gas feed stream.

£004 1 The air feed, can be any oxygen (<¾) containing gas suitable for use in the combustion furnace. Example gases suitable lor use as the air feed include air, oxygen- enriched air; pure 0¾, or a y eoinbinationihereo In at least one embodiment, the air feed .is air.

10643) I at: feast one embodiment, the air feed is ad usted such: that one-third of the HjS. present in the acid gas stream is burned to create SC¾ as shown In reaction (3) and 60%- 70% of the remaining ¾S is converted to elemental sulfur according to reaction (4). The combustion furnace can be any process unit capable of supporting the high . temperatures of the Claus thermal reactions, reactions (3) and (4). The combustion furnace operates at a temperature i the range of 900 "0 to 1400 hi at least one embodiment,- the tem erature lat e combustion furnace is greaier h n 983 Wit out being hound to particular theory, at temperatures greater than 9W G reaction (4), the endothermic formation of elemental sulfur is favored. The C!aus thermal reactions convert between 60 % by weight and 70 % by weight of the hydrogen sulfide and siilfur-contatning compounds present in the acid gas stream to elemental sulfur. A. furnace outle stream exits the combustion_, furnace. The furnace outlet stream can include ¾S, SO¾, CO* TfeQ, elemental sulfur , other gases, and combinations of the same.

190 4) The furnace outlet, stream exits the combustion furnace and is introduced to a waste heat boiler. The furnace outlet stream is at a temperature 'between 980 °C and 12O0¾ The; waste, heat, boiler can he any heat exchanger capable of removing heal from a stream and roduci g steam. The steam, produced in the waste best boiler can be high pressure steam (above 40 atm (4053 kPa}} or medium pressure stream (about 20 aim (2026.5 kPa), in at least one^■■embodiment, the waste heat holier produces high pressure steam. The waste heat boiler removes heat from tire furnace outlet stream to produce a cooled furnace stream.

_.[004$] The cooled furnace stream is -in a. gas state.. The: cooled furnace stream is fed to a sulfur condenser. The sulfur condenser removes heat from the cooled furnace stream causing the elemental sulfur present in ihe cooled furnace stream to condense .and form a liquid sulfur stream. The temperature in the sulfur condenser is between 100 °C and 200 , alternately between 110 X and 200 120 °C and 200 °C, 130 °C and 200 °C, and 140 °C and 200 X. The liquid sulfur stream can contain between 60 weight % and 75 weight % of the sulfur in the acid gas stream, and alternately between 65 weight. % and 70 weight % of the sulfur in the acid gas stream .

{0046] The components present in the cooled furnace outlet stream that do not condense leave the sulfur condenser as a first gas stream. The first gas stream can contain I¾S, St¾, 0¾, l¾()_f process gases, and combinations of the same_*-

P047 ^■Referring to FIGs. h% acid gas stream 100, air feed 10¾ lurnace outlet stream 103, cooled furnace outlet stream..105,. liquid sulfur stream 108, and first gas stream 106 can be understood. Combustion furnace , waste hea boiler 5. and sulfur condenser 6 can also be understood.

{0848] In a conventional Clays process, the first gas stream is feci to a series of two to three Claus catalytic stages. Each of the Clans catalytic stages includes a reheater, a catalytic reactor, and a condenser. The reheaters can be any heat exchanger capable of heating a gas stream from the condenser outlet temperature to the temperature at which the Claus catalytic reactions In the catalytic reactors occur, Due to the exothermic nature of reaction (I), the catalytic reactor temperature is lower in caci^subseq errt Qa alvt c reactor than the previous catalytic reactor. Without being bound to a particular theory, it is understood that the lower temperature in each subsequent catalytic reaetor takes advantage of the equilibrium nature of the reaction. The reaction temperature of the first .catalytic reaetor is the highest in order to. convert other sulfur_, species. The first reheater can heat the firs -gas stream to a first temperature above about. 205 °C. .sttemateJy. between about 205 °G and about: 346 °C, ^•alternately between about 2_.15 °C and about 340 °C, and alternately between about 225 °C and- about 340° C, In at least one embodiment, the first temperature Is about 235 "C. The second eliefer can heat the second gas stream to a. second temperature between 5 and 25 degrees below the first temperature, alternately between 10 and 2 degrees below the first temperature, and alternately between 15 and 20 degrees below the first temperature. In at least one embodiment,: the second temperature is 20 degrees less than the first ieiims atu ei In at bast one embodiment, the second temperature is 20 degrees less than the first temperature and the second temperature is 215 °C, The third reheater can heat the third gas stream, to a third temperature between 5 and 25 degrees below the second temperature, .alternately between 10 and 20 degrees beiow the second temperature, afid alternately ^'between 15 and 20 degrees below the second temperature. In at least one embodiment, the second .temperature i 10 degrees less than the first temperature. In at leas one embodiment, the second temperature is 10 degrees less than the first temperature and the second temperature is 205 °G. The specific temperature in each reheaier c n ^'be designed based on the .overall system.

£0049] In the catalytic reactors, the hydrogen Sulfide and sulfur dioxide are converted to elemental suffer and water according to reaction (I ), The catalytic reactors include a catalyst_, bed The catalyst in the catalyst bed of the catalytic reactors can be any catalyst that catalyzes reaction ( i}> The catalyst can include alumina, ^'.titanium dioxide, or combinations thereof Without being bound to a particular theory, i t Is observed tha reaction (1) produces primarily S§ from the reaetants !¾S and SO-?, whereas reaction :{4) produces primarily S-?. One of skill in the art will understand that both forms of sulfur, and ¾, are recoverable as liquid sulfur. A catalytic outlet stream exit each of the catalytic reactors and is fed to the condensers. The catalytic outlet stream can include elemental sulfur, ¾S, ¾0, SOj, other gases, and combinations of the same. The condensers can be .any heat exchanger capable of cooling, ea h of th catalytic outlet streams to a . ^'temperature: at which sulfur condenses to produce a sulfur stream, but above which water .remains as- a vapor. The sulfur stream includes liquid sulfur. I at least one embodiment the temperature in the condensers is between 1G C and 200 °C, The condensers can be designed to cool to temperatures at which ail of the sulfur is removed.

[0051 The Ciaus caialytie stages cm be understood, with reference to FiGs, 2 and 3. FIG,, 2 depicts a system with two Clans catalytic stages: a first Glaus catalytic stage includes first reheater 12. .first caialytie reactor 14, and first condenser .16; and a second Clans catalytic Stage includes second reheate 22, second catalytic reactor 24. and second condenser 26, Referring to FIG. 2 and as described, bove, first gas stream 106: is ted to first reheater 12 of the first Ciaus catalytic stage to create; first hot wet gas stream 212, First hot. wet gas stream 212 is- fed to first catalytic reactor 14 to produce first catalytic outlet stream 114. First catalytic outlet strea 114 is^■introduced, to first condenser 16, First condenser 16; condense elemental sulfur present; in first, catalytic outlet stream 114 to produce first sulfur Stream 118 and second gas stream 1 lb, Second gas stream 1,16: is fed to second reheater 22 to produce second hot wet gas stream 222. Second hot wet gas stream 222 is led to second catalytic reactor 24 to produce second caialytie outlet .stream 124, Second catalytic outlet stream 124 is introduced to second condenser 26. Second condenser 26 condenses elemental sulfur preseni in second catalytic outlet stream 124 to produce second sulfur stream 128 and tail ps stream 136. Tail gas stream 136 contains those gases that did not condense in second condenser 26.

|β052| .FIG. ^'3 depicts -a system with three Clays catalytic stages: a first Glaus catalytic stage includes .first: reheater 12, fjrst catalytic reactor 14. and first condenser 16; a second Clau-s catalytic stage includes second reheate 22, second catalytic: reactor 24, and second condenser 26; and a third Ciaus catalytic stage includes third reheater 32, third catalytic- reactor 34, and third ^'condenser .36, Referring to FIG- 3 and with reference to those elements described in connection with FIG. 2, in ; process with three Ciaus catalytic stages,, second condenser 26 produces second sulfur stream 128 and third gas stream 126. Third gas stream 126 : contains those gases that did not condense in second sulfur condenser 26. Third gas stream 126 is fed to third reheater 32 to produce third hat wet gas stream 232. Third hot wet gas stream. 232 is fed to catalytic reactor 34 to produce third catalytic outlet stream 134, Third catalytic outlet stream 134 is fed to third condenser 36. Third condenser 36 condenses the elemental ^'.sulfur in third catalytic outlet stream 1.34 to produce third sulfur stream i38_: and-

13

SUBSTITUTE SHEET RULE 26) tail gas stream 136, First hot wet gas stream 212 is at a higher temperature than second- hot wet gas stream 222 and second hoi wet gas stream 222 is at a higher temperature than thin! hot wet gas stream 33 in the: conventional Glaus processes described with ._..reference; to FIGs, 2 and 3, first gas stream 106, second gas stream 1 16, and third gas stream 126 and first hot wet gas stream 212. second hot wet gas stream 222, and third hot wet gas stream 232 contain- wafer vapor, j0053j. Advantageously, the present invention includes one or rnorc adsorber situated upstream of each of the Glaus catal tic stages, lie present invention can include one or fe wer adsorbers upstream of each of the reheaters of the Clans catalytic stage,

|ίΚΙ54] According to an embodiment of the present invention, the first gas stream exiting the sulfur condenser is fed to..an adsorber. The adsorber can remove water vapor from the gas stream to produce a dry gas stream and a water st.tx^sam, The adsorber can be any adsorption- dehydration eolunin unit designed to: remove: water vapor from &. wet gas stream, "Wet ps sirearn^"* as used herein, refers to a stream containing water vapor,

}0055| The adsorbe can _.include any molecular sieve capable of selectively- adsorbing water vapor from a wet^' as stream, while rejecting the remaining eomponents in the gas phase due to their larger molecular diameter. Molecular sieves operate b selectively adsorbing certain components in a stream. Molecular sieves suitable for use in the present invention have a pore size measured i Angstroms (A), Molecular sieves have a ^"crystal ^'lattice that results in a well-ordered pore and cavity structure. The effective channel diameter of the cages of the molecular sieve determines whether or .not a molecule with a certain kinetic diameter can .diffuse into the cage and be adsorbed. Any molecular sieve thai has an adsorption affinity , towards, water and a channel diameter small enough- to exclude hydrogen sulfide, but. large, - nough to allow water to pass through can be used.- Example of molecular sieves .-that cm he used in the present invention include ;zeo!ite-3A, Zeolite-IA includes a potassium zeolite, an effective channel diameter (pore diameter) of about A. and a bulk density of 44 pounds/cubic foot. The kinetic diameter of water is about 2.6A. Zeoiite-3A adsorbs water vapor and ammonia, Hydrogen sulfide has: a kinetic diameter of about 3 ,60 and Is not adsorbed by 2eoii†e-3A, Molecular sieve 3 can include a binder. In certain embodiments, the molecular sieve is produced by binding micron sized zeolite crystals together to form pellets, as is known in the art. The. binder can include silica or other Inert materials. Without being bound by a particular theory,, it is understood: that because the binder Is inert the performance of a molecular sieve is reduced proportionally to the amount of binder, It is understood that a pellet design can

without foregoing strength of th pellet For example, e equilibrium adsorption capacit of irtaleeuiar sieve with zeolite-lA pellets with b nder is ^'about 20 ercent by weight (wt %), & other words, 20·% of the total weight is water at equilibrium. The binder in molecular sieve 3 A can be about 9 weight %.

(0856] The amount of adsorbed water vapor molecules for a given adsorbent is a function of temperature and pressure. The amount of adsorbed water increases with, increasing pressure and decreases with increasing- temperature. Referring to FIG. ! ^'L the adsorption capacity for molecular sieve 3A at various tempera ures (adsorption isotherms) is provided. The adsorption capacity of molecular, sieve 3 A for water vapor at 100 °C is substantially higher than the adsorption capacity for water at 200 ^C,C. The temperature-, in the adsorber, is between 75 X and 170 X, alternately between 75 °C and 160 X,_. alternately between 75 X and 150 -X,,. and. alternately between 75 X and 140 X. In at least one embodiment, the. temperature of the adsorber is between 75 X and 150 X, The concentration of water in the dry gas stream is less than 1 part-per-mHIiors (ppm), alternately less than 0.5 pp¾ and alternately less than 0.1 ppm. In at least one embodiment the concentration of water in the dry gas stream is less than 0.1 ppm.

[8037] The .meth d for removal of sulfur includin adsorbers can. be understood with reference to FlGs, 1 and 4-9. FIG. I depicts a process with three Claus catalytic stages and an adsorber upstream of each of the Glaus catalytic stages. Referring to FIG. 1. and with reference to those elements described in connection with FIGs, 2 and 3, first gas stream 106 is ted to first adsorber 10. First adsorber 10 removes water vapor from first gas stream 106 to produce firs dry gas stream 110. First dry gas stream I S O is fed to first reheate? 12 to produce hot dry: gas stream 1 12. Hot. dry gas stream 11.2. is the absence of all or -substantially .all water vapor. As :used herein, 'in the absence of substantiai!y all water vapor" or "hi the absence of substantially ail of the water vapor" means that less than 1.0 ppm water vapor is in hot dry gas steeam 112., As used , herein "in the absence of water vapor" or "in the absence of all water vapor" means that the hot dry gas - ^'stream contains less than 0.1 ppni. First hot dry gas stream 1 12 Is fed to first catalytic reactor 1.4 to produce first catalytic outlet stream 1 14, Second gas stream 1 16 is fed to second adsorber 20. Second adsorber 20 removes water vapor front second gas stream 1 1 . to produce second dry gits stream 120. Second dry gas stream 120 is fed to second reheater 22 to produce second hot. dry gas stream 122. Second ho dry gas stream. 122 is in the absence of all or substantially all water vapor.

15

SUBSTITUTE SHEET RULE 26) Second hot dry gas stream 122 is fed to second catalytic reactor 24 to prqd ce second catalytic outlet stream 124., Third gas stream 126 is fed to th d adsorbei' 30. Third adsorber 30 removes water vapor from third gas stream 126 to produce third dr gas stream 130. Third dry gas stream 130 is fed to third reheater 32 to produce third hoi dry gas stream 1:32. ^■Hoi dry gas stream. 132 is in the absence of all or substantially all water vapor, Third hot dry gas stream 132 is fed to third catalytic: reactor 34 to produce third catalytic outlet stream 134, 058] First dry gas stream 110, second dry gas stream 120 and third dry gas stream 130 ate introduced to first reheater 12, second reheater 22,- and third reheater 3:2 respectively, to heat First dry gas stream I !0„ second dry gas stream 120 and third dry gas stream 130 to the reaction temperature in first catalytic reacto 14, second catalytic reactor 24, and third catalytic reactor 34, respectively.

|0I59] With reference- to F.lGs. I and 3. one of skill in the art understands that the compositions: of the, streams. :can- be the mm with respect to the components present, except for the presence of water vapor in certain streams that are not treated by an adsorber. As an example, first hot dry gas stream 1 12 can contain the same components as first hot wet gas Stream 212 except first hot wet gas stream 212 contains water vapor and first hot dry gas stream 112 is in the absence of water vapor.

{0060} The method for sulfur removal is in the absence of a condenser designed to condense water vapor from a gas stream. Advantageously, the use of molecular sieves for adsorption can remo ve all or substantially all of the water -vapor from a wet gas stream. The use of molecular sieves advantageously removes water to the ppm level as compared to a condenser whic can remove water to the saturation point for the operating temperai e and pressure, A condenser cannot be used to condense all or substantially all of the water vapor because the gas stream remains saturated with water vapor due to thermodynamic equilibrium, in a condenser, for any given temperature, the liquid water will be at equilibriu with/the vapor (the gas phase will be saturated water vapor},- because of this a condenser cannot remove enough wafer for the. purposes of the present invention. In a molecular sieve, the adsorbent can continue to adsorb water vapor and thus remove water until the adsorbent i saturated,

{806 ij Following the final condenser in d e system, the non-condensed components form a tail gas stream. The tail gas stream can contain ¾S, SO_¾€(¼, BaO, othe ases, and combinations of the same, Tail gas stream 136 can be fed to an. incinerator, can be vented to the atmosphere or an alternate process or altcrnaie process unit for removing contamtMnts fr m a stream.

10 62] A total conversion can be calculated from the total elemental sulfur recovered and the amount -of molecular sulfur in the acid gas stream. Total conversion can be between 99 wt

% and 99. wt %.

[6063] As used herein, "adsorber* refers to a two bed system, where at any time, one will be on an adsorption cycle and the second will be on a regeneration-cycle, la a pressure swing adsorption (PSA) system, .the^' regeneration cycle is drive by a decrease in the pressure in the regeneration bed compared to the pressure in the adsorption bed, causing components_, .to desorb. In a teraperatiire swi.ng_: adsorption (TSA) system, the regeneration cycle is drives by an increase, .in the temperature of the regeneration bed compared to the temperature in the ad&orptiott ted, causing components to desorb, A combination of PSA and TSA can also be used, The pressure in, the Glaus process is not high enough for a PSA without expensive compression ecjinpnient. Therefore, the present invention is in the --absence: of a PSA. process. A TSA s stem; ca be used in the present ^' invention, A T-SA can be better understood wit reference to FIG. 10, As shown in FiG. 10, gas stream 105 is ted to adsorption column lOA to produce- dry gas 1 10Λ. Adsorption column I OA is at temperature between 75 ^i:C and 170 °C, alternately between !,øø ¾ and 170 % and alternately between 100 °C an.d ISO °C. The residence time in adsorption column ΊΌΑ can be greater than. 2 hours and alternately between 2 hours and 12 hours. Adsorption column 1 OA contains molecular sieve 3A, Water vapor ¾ gas stream 106 is adsorbed b molecular sieve 3A leaving behind dry gas 110A. A portion of dry gas i_.IOA. is fed t ^'■ regeneration heater -10D and the remaining portion exits as dry gas stream I S O. Regeneration heater 10D increases the temperature of dry gas 1 1 OA to a temperature in the range between 175 ^DC and 260 °C to produce heated gas 110D. Heated gas H OD is led to regeneration column I OB, which increases the. temperature in regeneration column Ί0Β-. lire increased temperature in regeneration column i.DB causes water adsorbed On Molecular sieve 3A in regeneration column I6B to desorb. 1¾e.;dfi_.sq$jed water, -in the form of water vapor, is carried from regeneration column 10B as part of regenerated gas 110B. Regenerated gas 110B is cooled to a temperature below l OO^C to" form cooled stream 110E, Cooled stream U 0E is led to separator ί OF, where liquid water is separated from the gases in cooled stream H OE to produce water stream 1 10G and recycle gas stream I I OF, Recycle gas stream 11 OF is mixed with gas stream 166 and fed to adsorption column l OA, In certain embodiments, an adsorbe , siicn as a ^'ISA can Include a bu fer tank on the inlet stream, f 5)064] Through valves arid other piping components, the absorption c lumn can e switched to the regeneration column as needed,

EXAMPLES

{0065} The process of the present^' invention can be readily understood by Examples. The following examples wer simulated using a HYS Y^'S process simulator to simulate the method of the present ^' Mention... The simulations were based oh PIGs. 3-9 as indicated below and described above_* hi all of the Examples, acid gas stream 1.00 was simulated at a temperature of 3Q,0°C and_, a flow rate of 1 I ..0 kgraol/hr (3848.0; kg hr). Acid gas stream 100 had composition of 10,0,0.kmol/hr of hydrogen sulfide and 10,0.kmol/hr of carbon dioxide, The Bow rate of air feed 1,02 was automatically adjusted by the sirnulation so. com bustion furnace 3 had a simulated burn of one-m (1 3) of the h dro en: sulfide, present in aeid gas stream 100 wiife ah f om air feed 102 to produce S(¾, Combustion, furnace 3 operated in a range Ή9 1050 ¾. Gibbs energy minimization was used to simulate the; Clans thermal reaction, reaction (3), in combttStioft furnace 3 and the Clans catalytic reaction, reaction {I},, in the catalytic reactors 14, 24, and as applicable, 34, As applicable, adsorbers 10, 20, and 30 were modeled to 100% water vapor removal from gas streams 106, 1 16, and 126. Water vapor .removal of 100% is appropriate given hat molecular sieve 3A .can remove water vapor to the pprft level.

|0066] EXAMPLE 1. Example - _.1, a^■■comparative example, was simulated based n ^"Fl<3- 3, a process flow diagram of a conventional Claus process, including three catalytic reactors: first catalytic reactor 14, second catalytic reactor 24_> and third catalytic reactor 34, First reheater 12 increased the temperature of first gas stream 1.0.6 to a temperature of 235°C to produce ilrst hot wet gas : .stream 212. Second reheater 22 increased tte temperature of secon as stream i !6_: te temperature of 2 i5°C to produce second hot wet gas stream 222. Third reheate 32 inereased the temperature of ihlnl gas stream 126 to a temperature of 205 °C t produce third hot wet gas stream 232. The total sulfur recovered was 3137>8 kg/hr for a total conversion of 98. $ weight percept fwt *½} sulfur. 10067] Table 1; Stream properiies and results i« Example.!

^'\ EXAMPLE 1 -1 , Exat»pie 1 -1 is a MY SYS simulation according to HO, 4, a system having one adsorber immediately downstream of sulftir condenser 6. First adsorber 10 removed 78,2 fcgmol/hr (1409.0 kg/hr) of water from first: gas stream 106, First reheater 1.2 increased the temperature of first dry^' gas stream i 10 to a te perature .of 233*0· io produce first hot dry gas stream 1 12. Second reheater 22 increased the temperature of second gas stream 1 16 Co a tern per atiir of 215 to produce fi rsi hot wet gas stream 222. Third te eater 32 increased the temperature of third gas stream 126: to a temperature of 205 *C to produce second hoi wet gas stream 232. The total i¾r recovered was 3193.0 kg/hr for a iotai conversion of sulfur of 99.6 wt %.

{0069] Table 2: Stream Properties and esults Example 1-1

$070] Example 1 -2 is a HYSYS simulation according to F G. 5, a system having two adsorbers. First adsorber 10 emove 78.2 kgmoi br _:(i4:D9.0 kg/hrj of wafer from first gas stream 106. First reheater 12 increased the temperature of first dry gas stream: I- 1.0 to a temperature of 235°€ to produce first hot dry gas stream 112, Second adsorber 20 removed 18.6 kgmoJ/hr. (335.6 kg/hr) of water from second gas s eam 1 16_* Second reheaier 22 increased the temperature of second dry gas stream 120 to a temperature 0f2! 5°C to produce .second- hoi dry gas stream 122, Third reheater 32 increased the temperature of third; gas stream 126 to a temperature of 203 % to produce firs hot wet gas stream 232. The total sulfur recovered was 3203,6.0 kg ^'hr tor a total conversion of sulfur of 99,9 \vt %.

{00711 Table 3; Stream properties la Example 1 2

[0072} Example 1 -3 is a HYSYS simulation according to FIG. 1, a system having three adsorbers. Adsorber 10 removed 78.2 kgmol hr (1409.0 kg/hr) of water from first gas stream 106, First reheater 12 increased the temperature of first: dry gas stream 110 io a temperature of 235°C to produce first hot dry gas s ream 1 12. Second adsorber 20 removed 18,6 kgmol/hr 33 - kg.½i of water from s cond gas stream 1 16, Second reheater 11. increased the temperature, of second dry gas stream 120 to a temperature oOlS'C to produce second hot dry gas stream 122. Third adsorber 30 produced 3.0 kgmol/hr (53 ,3 kg/hr) of wafer from third gas stream 126. Third reheater 32 increased the temperature of third gas stream 1 6 to a temperatur of 205 °C t produce third hot dr gas stream 112. The total sulfur recovered was 32063.0 kg/hr for a total conversioii. of sulfor of 100.0 i %, 0073} Tahie 4; Stream properties I» Exampl .1 3^'

0,0001 i 6.000 0.600 (ixm

Example 1-4 is a HYSYS simulation according to FIG, 6 having due adsorber upstream of the fma! Claus catalytic stage. First reheaier 12 increased the temperature of first gas stream 106 to a temperature of 235*C to produce first hot vvei gas stream 212, Second, reheats? 22 increased the teffi:perature; 0f second gas stream 11:6 t a temperature of 2 iS^QC;to produce second hot wet gas ^' sirearn 222, First ad er 10 removed 98.1 kgmol hr (1767:1) kg/hr) of water from third^■gas: stream 126. Third reheaier 32 increased, the tem erature of first dry gas stream 1 10 to a .temperature of 205 ^<SC to produce fi st hot dry gas stream 132. The total sulfur recovered was 3202,6 kg/hr for a total conversion of 99,9 wt%,. i §7S| able St Stream properties n Example 1-4

[Wl-fy The results of Examples ! through 1 : mclieaie that the adsorbers increase the porivefstoii o sulftsr i« the catalytic reactors. Table 6 is a comparison of the results,: Havin even one adsorber to remove water from the process increases the conversion b at least t% over the sy stem In Example 1 that had. no adsorbers. j¾87fj Ta&le 6. Comparison of sislftir trshm

[ β7δ| EXAMPLE 2. Example 2. a. comparative example. Is HYSYS simulation ccording to FIG. I, a process flow dsagmm of a cosve kMial Clans process, Including two catalytic reactors; first catalytic reactor 14 and second catalytic reactor 24. First reheater 12 increased the temperature of first gas stream 10 to a emperature of 235?G to produce first hot we ; : as: :sire»S : 212, Second reheafer 22 increased the temperature of second gas siream 116 te a temperature Of 205*6 to: produce second hoi wet gas sireara 222. The total syf&r ^■recovered was 3157. S fg/hr ibr a tota eon version of 9? . S _:wt %. f 0079] Table 7, St ream properties and results far Example 2

1 } Example .2-1 iis . a BYSYS simulation according to FIG. 7 havin - m adsoriw upstream of the first Glaus catalytic stage. First adsorber 10. removed kgmo!/hr (1409.0 kg/hr) of water^' from first gas stream. 106. First reheater 12 increased the temperature of first dfy gas stream 1 S O to a iemperatiffe of 23.5°C to produce first hot dry gas -stream _.1 12, Sec nd reheaier 22 increased the tem perature of second gas stream 1 16 to a temperature, of 205^¾C to produce first hoi wet gas stream 222. The total sulfur recovered was 328,1.3 .kg hr for a total ^■conversion of 99,2 wt ¾..

[MM] Tafe e S. Stream properties and results for xam le 2-1

l82J Example 2-2 is a HYSYS simiiiatiDri according to FIG, 8 having two adsorbers. •First .adsorber 10 removeii. 78.2 kg!iio hr (1.409.0 kg/hr) of water from first gas stream 106. First rebeater 12 increased the temperature of first d y gas stream. 110 to a temperature of 23$¾ to p oduce first: hot drv gas stream 112. Sec nd adsorber 20 removed 18,6- kgraol hr (335,6 kg/hr) of water from second gas stream 116, Secon reheater 22 Increased the temperature of second dry gas stream 1.20 to a temperature of 20§°C to produce second hot dry gas strearn 122, Tte total sulfur recove ed was 3199.6 kg hr tor a total e nversioft of 99J :wt %.

Tsble Btv properties aoti results for Examp 2-2

(0084] ^'Example 2*3_. is a HYSYS simulation according to FIG. 9 having one adsorber upstream of the final Glaus catalytic stage. First reheater 1.2 Increased the temperature of first gas stream 106 to a temperature of 23S°C to produce hot wet gas stream 212. Adsorber SO removed 94.0 ^'kgmpi hr (1693,0 kg hrj of water from ^'second gas stream 1 16. Second reheater 22 increased the temperature of dry gas stream 1 10 to a temperature of 205 to produce hoi dry gas stream .122, The ai sulfur recovered was 3190,2 kg hr f¾r a total

Table 16. Stream rope ties »»d reswlis for Exam le 2-3

[0086] The results of Examples 2 through 2-3 indicate that the adsorbers increase the conversion of sulfur in the catalytic reactors. Table 1.1 is a comparison of the results. In a Glaus process having two Class catalytic stages, ever? one a s rber can Increase the siiifar recovery, so that the Cfeiss process can achieve greater than 99 w % removal of sulfur^';

}M87j Table 1 1. Comparison ..of sulfur canversion

{0088) If the minimum ^' requirement: for hydrogen sulfide coo version is .99-5 vvt%, all of the Examples u in adsorbers achieve the minimum requirement except the two C^'iaus catalytic stage wit only one adsorber upstream of the first Ciaus catalytic stage. The Example illustrate ^'that the removal of water by adsorbers in addition to the ^'removal of sqlfu^'r in the condensers increases the conversion in the Glaus catalytic reactors,

Although eml idiments have been described in detail, it should be: understood that various changes, substitutions, and alterations can be made without departing from the principle and scope of the inveniipn. Accordingly, the scope should be determined b the following claims and their appropriate legal equivalents.

29

UBSTITUTE SHEET RULE 26) }¾©9¾. The:^■ singular f rins and ^'*¾© include plural referents, iiBless t e context dearly dictates otherwise,

[KMf "Optional" or "^ t ftsiy"^' means thai the subsequently described event or ekcurnstances eaa or may not occur. The description includes instances where the: event or eii^'C«i¾stanee occurs and instanees where it. does net occur.

[092] Ranges may he expressed tHrough¾ut.¾s fx0m..-at> «i one particular value to about another particular value. When such a range is expressed, it is to be u erstood that ^'another embo iment is front the one particular value to the other paiticul t value, along^', with.. sU combinations^" i- Jitn said range, Q¾93| As used throughout and in the appended claims the words "'comprise/^' ·¾¾* ·· and "include" and all grammatical variations: thereof ate each intended to have an open, oon- !ffititing meaning that, does not exclude additional elesfients or steps, f(M$4j As m&& throoghont, terms such as: ^firsi and "second" are assigned based on the; position of the anil in the Sow; path and are merely intended to differentiate between two..or more of the same units: h system:. It is to be understood that the words "first" and "second" serve- no other purpose and are not pari of the name or- description of the c mg ment S¾thennore-, it is to be understood that thai th mere use of the term "first" and "second" does not require tha there he any "third" component, although that possibility is conte plated under the scope.

Claims

CLAIMS What is claimed is:

1. A method to recover sulfur from hydrogen sulfide in an acid gas stream, the method comprising the steps of:

feeding the acid gas stream to a combustion furnace to produce a furnace outlet stream, the combustion furnace configured to convert the hydrogen sulfide to elemental sulfur, wherein the furnace outlet stream comprises elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor;

introducing the furnace outlet stream to a waste heat boiler to produce a cooled furnace outlet stream, the waste heat boiler configured to reduce a temperature of the furnace outlet stream;

condensing the cooled furnace stream in a sulfur condenser to produce a liquid sulfur stream and a first gas stream, the sulfur condenser configured to reduce a temperature of the cooled furnace stream to a temperature below a dew point of elemental sulfur and above a dew point of water;

feeding the first gas stream to a first adsorber to produce a first dry gas stream and a first water stream, wherein the first adsorber comprises a molecular sieve, wherein the first dry gas stream is in the absence of water vapor, wherein the first dry gas stream comprises hydrogen sulfide and sulfur dioxide;

heating the first dry gas stream in a first reheater to produce a first hot dry gas stream, wherein the first hot dry gas stream is at a first temperature;

feeding the first hot dry gas stream to a first catalytic reactor to produce a first catalytic outlet stream, wherein the first catalytic outlet stream comprises elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor;

cooling the first catalytic outlet stream in a first condenser to produce a first sulfur stream and a second gas stream, the first condenser configured to condense the elemental sulfur in the first catalytic outlet stream such that the first sulfur stream comprises liquid sulfur, wherein a temperature in the first condenser is between the dew point of sulfur and the dew point of water, wherein the second gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor;

feeding the second gas stream to a second adsorber to produce a second dry gas stream and a second water stream, wherein the second adsorber comprises a molecular sieve, wherein the second dry gas stream comprises hydrogen sulfide and sulfur dioxide, wherein the second dry gas stream is in the absence of water vapor;

heating the second dry gas stream in a second reheater to produce a second hot dry gas stream, wherein the second hot dry gas stream is at a second temperature, wherein the second temperature is lower than the first temperature;

feeding the second hot dry gas stream to a second catalytic reactor to produce a second catalytic outlet stream, wherein the second catalytic outlet stream comprises elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor;

cooling the second catalytic outlet stream in a second condenser to produce a second sulfur stream and a third gas stream, the second condenser configured to condense the elemental sulfur in the second catalytic outlet stream such that the second sulfur stream comprises liquid sulfur, wherein a temperature in the second condenser is between the dew point of sulfur and the dew point of water, wherein the third gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor;

introducing the third gas stream to a third adsorber to produce a third dry gas stream and a third water stream, wherein the third adsorber comprises a molecular sieve, wherein the third dry gas stream comprises hydrogen sulfide and sulfur dioxide, wherein the third dry gas stream is in the absence of water vapor;

heating the third dry gas stream in a third reheater to produce a third hot dry gas stream, wherein the third hot dry gas stream is at a third temperature, wherein the third temperature is lower than the second temperature;

feeding the third hot dry gas stream to a third catalytic reactor to produce a third catalytic outlet stream, wherein the third catalytic outlet stream comprises elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor; and

cooling the third catalytic outlet stream in a third condenser to produce a third sulfur stream and a tail gas stream, the third condenser configured to condense the elemental sulfur in the third catalytic outlet stream such that the third sulfur stream comprises liquid sulfur, wherein a temperature in the third condenser is between the dew point of sulfur and the dew point of water, wherein the tail gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor.

2. The method of claim 1, wherein a total conversion can be determined.

3. The method of claim 2, wherein the total conversion exceeds 99 % by weight.

4. The method of any of claims 1-3, wherein the molecular sieve is molecular sieve 3 A.

5. The method of any claims 1-4, wherein the first temperature is 235 °C.

6. The method of any of claims 1-5, wherein the second temperature is 215 °C.

7. The method of any of claims 1-6, wherein the third temperature is 205 °C.

8. A system to recover sulfur from hydrogen sulfide in an acid gas stream, the system comprising:

a combustion furnace, the combustion furnace configured to convert the hydrogen sulfide to elemental sulfur to produce a furnace outlet stream, wherein the furnace outlet stream comprises elemental sulfur, hydrogen sulfide, sulfur dioxide, and water vapor;

a waste heat boiler fluidly connected to the combustion furnace, the waste heat boiler configured to remove heat from the furnace outlet stream to produce a cooled furnace stream; a sulfur condenser fluidly connected to the waste heat boiler, the sulfur condenser configured to condense the elemental sulfur in cooled furnace stream to produce a liquid sulfur stream and a first gas stream, wherein the gas stream is in the absence of elemental sulfur, wherein the first gas stream comprises water vapor;

a first adsorber fluidly connected to the sulfur condenser, the first adsorber configured to remove water vapor from the first gas stream to produce a first dry gas stream and a first water stream, wherein the first adsorber comprises a molecular sieve, wherein the first dry gas stream comprises hydrogen sulfide and sulfur dioxide and is in the absence of water vapor;

a first Claus catalytic stage fluidly connected to the first adsorber, the first Claus catalytic stage configured to produce a first sulfur stream and a second gas stream;

a second adsorber fluidly connected to the first Claus catalytic stage, the second adsorber configured to remove water vapor from the second gas to produce a second dry gas stream, wherein the second adsorber comprises a molecular sieve, wherein the second dry gas stream comprises hydrogen sulfide and sulfur dioxide and is in the absence of water vapor; a second Claus catalytic stage fluidly connected to the second adsorber, the second Claus catalytic stage configured to produce a second sulfur stream and a third gas stream; a third adsorber fluidly connected to the second Claus catalytic stage, the third adsorber configured to remove water vapor from the third gas to produce a third dry gas stream, wherein the third adsorber comprises a molecular sieve, wherein the third dry gas stream comprises hydrogen sulfide and sulfur dioxide and is in the absence of water vapor; and

a third Claus catalytic stage fluidly connected to the third adsorber, the third Claus catalytic stage configured to produce a third sulfur stream and a tail gas stream.

9. The method of claim 8, wherein a total conversion can be determined.

10. The method of claim 9, wherein the total conversion exceeds 99 % by weight.

11. The method of any of claims 8-10, wherein the molecular sieve is molecular sieve 3A.

12. The system of any of claims 8-11, wherein the first Claus catalytic stage comprises: a first reheater fluidly connected to the first adsorber, the first reheater configured to increase a temperature of the first dry gas stream to produce a first hot dry gas stream, wherein the first hot dry gas stream is at a first temperature;

a first catalytic reactor fluidly connected to the first reheater, the first catalytic reactor configured to convert hydrogen sulfide and sulfur dioxide to elemental sulfur to produce a first catalytic outlet stream, wherein the first catalytic outlet stream comprises hydrogen sulfide, sulfur dioxide, elemental sulfur and water; and

a first condenser, the first condenser fluidly connected to the first catalytic reactor, the first condenser configured to condense the elemental sulfur in the first catalytic outlet stream to produce a first sulfur stream and the second gas stream, wherein the second gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor.

13. The method of claim 12, wherein the first temperature is 235 °C.

14. The system of any of claims 8-13, wherein the second Claus catalytic stage comprises:

a second reheater fluidly connected to the second adsorber, the second reheater configured to increase a temperature of the second dry gas stream to produce a second hot dry gas stream, wherein the second hot dry gas stream is at a second temperature;

a second catalytic reactor fluidly connected to the second reheater, the second catalytic reactor configured to convert hydrogen sulfide and sulfur dioxide to elemental sulfur to produce a second catalytic outlet stream, wherein the second catalytic outlet stream comprises hydrogen sulfide, sulfur dioxide, elemental sulfur and water; and

a second condenser, the second condenser fluidly connected to the second catalytic reactor, the second condenser configured to condense the elemental sulfur in the second catalytic outlet stream to produce a second sulfur stream and the second gas stream, wherein the second gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor.

15. The method of claim 14, wherein the second temperature is 215 °C.

16. The system of any of claims 8-15, wherein the third Claus catalytic stage comprises: a third reheater fluidly connected to the third adsorber, the third reheater configured to increase a temperature of the third dry gas stream to produce a third hot dry gas stream, wherein the third hot dry gas stream is at a third temperature; a third catalytic reactor fluidly connected to the third reheater, the third catalytic reactor configured to convert hydrogen sulfide and sulfur dioxide to elemental sulfur to produce a third catalytic outlet stream, wherein the third catalytic outlet stream comprises hydrogen sulfide, sulfur dioxide, elemental sulfur and water; and

a third condenser, the third condenser fluidly connected to the third catalytic reactor, the third condenser configured to condense the elemental sulfur in the third catalytic outlet stream to produce a third sulfur stream and the third gas stream, wherein the third gas stream comprises hydrogen sulfide, sulfur dioxide, and water vapor.

17. The method of claim 16, wherein the third temperature is 205 °C.