(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) eae ee eee NOOO International Bureau, fort een ee (10) International Publication Number Secenber:010(3.122010) per WO 2010/141496 A3 COIR ME 2006 01) ROD $4782 2006.01) [USIUS); 36 Jol Janes Audabo Way, Matton, NI (08083 (US). RABINOVICH, Alexander [USUS} 235 20) International Application Number: ee reared ies PCTUS2010036941 (74) Agents: GESS, Joseph, I 3; Merchant & Gould PC 808. Steet, Minneapolis, MN 55402 (US) (81) Designated States (nless otherwise indicate, for every (22) toternatonal Fling Date 1 June 2010 (01.06.2010), 25) Filing Language: Egish 1" kind of rational protection varlabe): AE, AG, ALAM, (26) Publication Langu English AO, AT, AU, AZ, BA, BB, BG, BH, BR. BW, BY, BZ. (CA, CH, CL, CN, CO: CR, CU, CZ; DE, DK, DM, DO, Gt) Priority Dats x < DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, syianas 1 Sune 2009 (01.06.2009) USN, HR HU, ID. TL IN. 1. JP, KE, KG, KM, KN, KP. 2790280 May 201028052010) US RRC RA EAC LGL EK. LR LS-LTLU. EY. MU MD, OV) Applicants for all designated States evwepr US MEL MG, MK, MN, SW, MIX, MI, MZ, NA, NG, NI BNO Usa INC CUSUST cont eninge NOLNZ. OM,BE,PG, PIL PL, PT. RO. RS, RU, SC SD, SE,SG,SK, SL, 8M, ST, SV, SY, TH, TI, TM, TN, TR Canyon Road, San Rafiel, CA 94852 (US), DREXEL le eee TTT, TZ, UA, UG, US, UZ, VEN, ZA, 2M, 2 UNIVERSITY [USUS], 3141 Chest So, Palade! hi, PA 19104 (US). (84) Designated States fanless otherwise indicate, for every find of regional provetion availabe: ARIPO (BW, GH, GM, KF, LR. LS, MW, MZ, NA, SD, SL, SZ TZ, UG, 2M, ZW, Fuss (AM, AZ, BY, KG, KZ, MD, RU 1 ‘TMD, European (AL, AT, BE, BG, CH.CY, CZ, DE, DK, (72 Inventors: and CA 54582 (US) POTTER. R., Witlam [UStS), 207 TMD, Eawpean AL, AT BE BG, CUE CY. CZ, DE: DK. Heritage Lane, Pkaseatoa, CA'94566 (US). GUTSOL, FE: BS 5B. Gi I. IS, TE, LT, LU, Fa eS Se ea eae GUTSON LY, MC, MK, MT, NL, NO, PL, PT, RO, SE, SI SK Philadelphis, PA 19104 (US). NUNNALLY, ‘Thomas C1 CM, GA. GN. GQ, US/US, 4007 Lasrsiou Stee, Philbdeipia, PA 19128 ‘SM, TR), OAPL(BE, BJ, CF, CG GW, ML, MB, NE, SN, TD, 76), 1Cuninued on next pagel le: METHODS FOR LOW TEMPERATURE HYDROGEN SULFIDE DISSOCIATION 80 400 Energy Cost (evil) 200 ‘ooo omens) Energy Input (evi FIG. 1 (67) Abstract: A matbod OF LS dissociation comprises generating radicals o¢ fons. HS dixosiaton is nto at relatively low femperse of less than 1875 K. The resifence time for dissociation acer anges fom about D1 4 10 In nee bodiment, plasmas ae used to genorate ons for us inthe HS dissociation, 2 2 ~ & 3S = = S & ° =WO 2010/141496 A3 IIE MMI Published! (88) Pate of publication ofthe international search report: 17 February 2011 with intemationat search report (Art. 213)) = Infor the expiration ofthe tine litt for amending the clans and ae republished the vent of rece oF damendiaens (Rule 48.218)WO 2010141496 PCT/US2010/036941 Methods for Low Temperature Hydrogen Sulfide Dissociation BACKGROUND Hydrogen sulfide, HS, isa byproduct of oll refinement, Therefore, efficient HLS, ‘eatment and utilization is erucial tothe ol and gas industry. In particular, HS dissociation into sulfur and hydrogen is commercially important forthe ol and gas industry, which consumes large amounts hydrogen in oil hydrotreatment Rising fuel costs and more stringent restrictions on CO; emissions have resulted increasing interest inthe weakly endothermic process of H.S dissociation, which can be arranged in a chemical or thermo-chemicl reactor and caried out ia the following renction: TS > Hi, + Sy; AHys ~ 20.6 Ki /inole ~ 0.213 eVimol ~ 0.255 kWa'm? (1). From the standpoint of thermolynamies, HS isa cost effective source of hydrogen, a the Aisassociaton eneray oF HS is only 0.2 8V per molecule, Therefore, the possibility 10 Aisocite HLS int sulfa and hydrogen is important commercially. Ithes been estimated that i plasma dissociation of H:S ean be industrially realized with Specific Eneray Requiroment (SER) lower than | eV per H: molecule, the rofning industry can save upto 70:10 Bealye, Several plasma-chemieel systems have ben utilized for HLS dissociation: microwave (MW) discharge, radio fequency (RF) discharge, sliding are (GA) discharge, gliding arin tornado (GAT), and nitrogen plasma je. Such plasma-chemical systems however, have significant drawbacks. Powerful MW systems are no readily available and are complicated and expensive. Both MW and RF discharges are dificult w arrange at elatvelybigh pressure wi he presence of inydrogen inthe plasma. Scaling up of these systems is also problematic. GA and conventional ar discharges have elatively low efficiencies, GAT and conventional GA have potential problems with elect deterination end lso problems with sealing, Dissociation in the nitrogen plasma jt alo has relatively low efiiency and erates unnecessary byproducs (NHS). The existing theoretical basis for HS dissociation wes developed in the 1980's, when detailed kinetic simulation was dificult because of Tow computational power, It wasWO 2010141496 PCT/US2010/036941 concluded thatthe process is defined by equilibrium heating, The tauitional kintie scheme (oF HS dissociation includes one endothermic reaction: HSS +Mo SH+H+M; As 93 eVimol 2) 79 Kulm Which isthe limiting reaction inthe Scheme, and several fast exothermic resctions: HHS eH: SH @) SH+SH H+: (4) SHI SHO IS +8. (5) HS+SOH+S: ©. As result is necessary to spend 3.95 eV to dissociate two molecules of 12S, which is equivalent to SER of hydrogen production a least 1.968 eV/mol. ‘Thermelynamic ‘equilibrium modeling withthe assumption of plug flow reactor with fast preduct quenching shows the lowest SER that can be expected is 2.04 eV per molecule (Soe Figure 1), which is achieved at 1875 K, Table 1 shows the composition of an equilibrium HyS mixture atthe point of minimum SER (species with mole faction lower than 0.1% omitted), Table | “Mixture Species” Mole Fraction a) 1S T99 191 50.98 24.98 More efficient and effective processes for H,S dissociation would therefore be of ‘great benefit to the oil and gas industry.» WO 2010141496 PCT/US2010/036941 SUMMARY Provided isa method of HS dissociation comprising generating radicals or ions, Wherein HS dissociation is initiated ate relatively low temperature, eof less than 1900 K, for example, less than 1875 K, or less than 1700 K. none embodiment, the process involves reactions with the accumulation of H product and using a reaction chain that i triggered with a small amount of H and SH radicals, Im another embosiment, plasms catalysis is used. lons are produced in or introtuced into a reaction zone of elatvely low temperature. Positive and negative charges can be prevented from recombining by ercating « DC corona discharge in the reastion zone, or by applying a biased voltage BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWING Figure | shows SER of dissociation per H:S molecule as a function of energy input according to a thermodysamic equilibrium simulation withthe assumption of plug flow reactor with fest produet quenching. Figure 2 illustrates the presently disclosed chemical kinetics mechanis dlissocistion and formation of H:S2 88a procuct Figure 3 shows the modeling results of HoS and Hs mass fraction as function of temperature, Figure 4 shows SER of dissociation as a function of eneray’ input for thermodynamic equilibrium and kineties modeling. Figure Sis a dingram of basic reactor schematic. Figure 6 isa disgram of dissociation eactor with a heating element Figure 7 isa dingram of e dissociation reactor with corona discharge Figure 8 is dingram of & dissociation reactor with glow discharge. Figure 9 isa diagram of e dissociation reactor with DC corona, Figure 10 is a diagram ofa dissociation reactor with DC plasma and bissed cylindrical DETAILED DESCRIPTIONWO 2010141496 PCT/US2010/036941 Methods for HS dissociation are provided based on modeling and the analysis of high efficiency results obiained in MW, RF, and GAT systems. Acconting tothe presently disclosed methods, H:S dissociation can be initiated at temperatures that are significantly lower than those that are needed 0 reach the minimum SER aceording to thermodynamic equilibrium modeling with the assumption of plug flow resctor, ‘The presently disclosed methods are based upon presently disclosed chemical kineties mechanisms for H:S dissociation that enable low temperature dissociation, One mechanism, replaces the major dissociation product S. with H:S), which ean farther release hydrogen and leave sulfur asa final product at lower temperatures, Otter mechanisms involve molecular or cluster ions for plasma catalysis ‘Chemical Kinetics Mechanism ‘The presently disclosed chemical kineties model shows the possibility of low SER for HLS dissociation at temperatures that are sigaificantly lower than in earlier models. The presently disclosed chemical kincties mechanism, witha list of parameters, is shown in Table 2 Rexetion St MoSH+ HTM HSSH+S WS +Weo i +st HS +84 28H SH+SOH+S: SH+H OH +S SH#SHO H+ SH+SH OHS +S SH+HS HS: +H HS:+MoSH+SH+M StMoS+S+M ‘Table? A,em"/molecules DORE 3.1610 2318-07 1386-10 4.00E-11 301E-11 1008-14 1.S0E-11 332F-10 3436.07 7.95E11 7a 0.00 Lo 0.0 0.00 0.00 0.00 0.00 ost 100 0.00 kcal/mole 66.21 65.49 0.90) 7.392 0.00 0.00) 0.00 0.00 27.00 sTa2 76.96WO 2010141496 PCT/US2010/036941 So4S 4M eo StM 2236-29 0.00 Hot MoH +H4M 3.70E-10 0.00 HSSHSSGHsS:+S; 346E-15 237 HS +HSS HLS +S: 3.66E-13 3.03 H+HSSoS+HS 7326-11 0.00 H+HSS +H. +S: 2SIE-I2 16s S+HSS HS +S: 2.006-2 2.20 -0.60 ‘Main features of the presently disclosed chemical kinties mechanism are accumulation of HS: as product and the reaction chain thet is triggered with a small amount (-11%) of H and SH radicals (see Figure 2). Another mein feature is thatthe process yiekls significantly higher dogree of H,S dissociation than the thermoxlynamic equilibrium modeling ‘with the assumption of plug flow reactor with fast product quenching, ‘The modeling results ‘of dependence of mixture composition from the initiston wemperature are ilustated in Figure 3 The thermodynamic equilibrium mixture composition is also shown for comparison. ‘The modeling was performed on Chemkin® 4.1.1 software suite using a single adiabatic plug flows reactor with the initial mixture composition kept constant at 98% Ho, 1% SH, and 1% # ‘The above fextures contribute to the very low SER of HLS dissociation using the presently disclosed chemical kinctcs mechanism, The mininsum SER corresponding to the initiation temperature OF L175K is 0.609 eV/nol, wi slower than ‘minimum SER predicted by thermodynamic equilibrium modeling with the assumption of plug flow reactor with fast product quenching. A comparison of the results from both more dhan three kineties and thermodynamic equilibrium modeling is show in Figure 4, H:S: should be considered asa final product of geseous phase kinetics. Further dissociation of sulfanes (H4:S.) with hydrogen and sulfur release takes place at much lower temperatures in the condensed phese. ‘The presently disclosed chemical kineties mechanism shows significant improvement ‘over previous models (e.g, conventional thermodynamic equilibrium model with the assumption of plug flow reactor with fast produet quenching) and provides & potentialWO 2010141496 PCT/US2010/036941 explanation for the low dissociation SER observed in MW, RF, and GAT expe: “which energy consumption was half of the SER 2.04 eV per molecule expected according, nents, in to conventional thermodynamic equilibrium modeling withthe assumption of plug flow reactor with fast product quenching, HS dissociation at low temperatures is possible and leads to significantly higher lissociation rate than in previous models, Hz dissociation at low temperatures requines rather long residence time ranging from 0.01 to 10 seconds (s), for example, from 0.L 10 Ls, depending on the temperature ofthe process. The residence time drops sharply with temperature increase. Plasma-Catalytic Mechanism Another presently disclosed mechanist involves so-called plasms catalysis. The simplest example isan introduction ofthe ion-molecular reactions (that ususlly do not have any energy barsiers) HS + Sy" 9 H+ 8; + SH"; Alyy ~ 316 ki/mol ~3.28 eVinolee (7) SH + SH! > Hp + S31; AH = -89.2 klimol = -0.925 eV/molee (8) together with reetion (3) allows to decrease the enthalpy ofthe liming reation (compare reactions (7) and (2). “Much more significant decrease of the reaction temperature ean be expecta ifs assumed that negatively or positively charg sulfur elusters play eatalysis role fr the grows reaction (1), for example Sy! + HS > Hs + Sea's AHL $20.6 kd/mol = 0.213 eVimolee = 0.255 kW-him? (9). While there is no available data to estimate possible rate and efficiency of this reaction, a Similar reaction plays a key role in the mechanism oF Si nano-particles formation in SiHL-Arplasma, Therefore, non-equilibrium plasma processes may play key roles in effective HS dissociation, and reaction control should be possible through the control of plasna parameters. For effective realization ofthis mechanism it is necessary to produceWO 2010141496 PCT/US2010/036941 1 ions in (or introduce into) the cone of relatively low wmperature where the reaction (9) is 2 much faster then the reverse reectons. Also itis important to separate positive and negative ‘5 charges to prevent their fist recombination, This can be arranged, for example, by creating 4 DC corona discharge inthe resetion zone (Fig. 9) of by applying biased voltage between 5 contra plasm zone end a cylindrical wall (Fig, 10), 7 Apparatus and Method for Low Temperature H:S Dissociation s ‘ased on the presently disclosed numerie modeling results and analysis ofthe 9 presently disclosed plasma-catalytic mechanisins, there are several ways of organizing an 10 HS dissociation reactor (se figures 5-10). For most cases, a reactor will operate with the 11 following general parameters: relatively low reaction zone temperature (less than 1900 K, in 12 particular, less than 1875 K, for example, less than 1700 K), long residence time (irom 0.01 131 10s, forexample, from 0.1 10 1), and a low power dissociation source for generation of 14 Hand SH radicals or ions. The frst two parameters are common for all the reactors and can the main factor 18 be organized almost identically forall the reactors. The dissociation source 16 distinguishing he reactors and requires significant changes from one reactor to another, ” ‘The long residence time in the reactor can be achieved by extending the length of the 18 reaction zone proportionally with desired operstional flow rates, For example, the laboratory 19 size reactor designed! to operate at 1 V/min oF pure H,S ean have the reaction (hot) zone of I m 20 witha residence time of I s, which corresponds to eross-section of 0.167 em’ or, inthe case ‘of cylindrical reavtr, the diameter of 0.46 em, Such system, even under laboratory concltions, can be scaled to accept 10 times higher flow rate by increasing the diameter of the 23° reavtora little more than 3 umes to 1.45 om, 2 ‘The uniform temperature ofthe mixture in the range from 800 K to 1700 K can be 25 maintained throughout the zeaction zone by heating the reaction zone extemally with 9 26 convenient and efficient power source, e.g. heat exchanger, or by mixing with hot hydrogen. 27 Forexample, a high quality tube furnace can be used for this purpose (Figures 5.9). Still, 28 special care should be taken while choosing the main reaction chamber due to the heating, 29° requirements. For example, the reaction tube can be made out of quartz or eeramie, whieh share high melting temperauire, and both ean be used as a dielectric, which is one oF the S31 requirements for the local dissociation source, Figure 5 shows a gencral schematic of &WO 2010141496 PCT/US2010/036941 simple plug-flow reactor with extemal furnace and without local disso comprising reactor tube 1, inet flange 2, inet 3, closed end flange 4 and heating elements 5, Several types of the reactors (Figures 6-9) can be distinguished based on the type of the source that is used for local H:S dissociation, Even though some of the reactors have significantly different underlying prineipes, al ofthe reactors share & low power requirement, In general, power for the local dissociation should not exceed SU"6, for example, 10%, of total power ofthe process: local dissociation plus external heating. Low current less than SA, eg. less than 1A, are or glow discharge is also appropriate at pressures between 0.01 MPa and IMPa, ‘The concept af radical production tarough localized heating is based on the presently disclosed chemical kinetics mechanism, but with the consideration that relatively high ‘temperatures (of less than 2000 K, in particular, less than 1875 K) are reached in a very sill volume with minimal energy input. Such high temperatures allow for very fast (ane to two ‘orders of magnitude faster than in theres ofthe reactor volume) HS dissociation on H and SH radicals or generation of ions that sequentially trigger the ehain reactions in the entire volume of the resetor. Figure 6 shows a schematic oF a reactor based on localized heating comprising high temperature heating element LI (hot wire) and power supply 12. Other sourses of radicals eg, small hydrogen dissociator or hydrogen plasma injection ean be used. ‘A possible plasma source for low power radical production is cosona discharye. Its ‘organized along a thin condvetive wire plaved along the axis ofthe reactor, ‘The physival properties ofthe wire are important duc to the relatively high tomperstures that the wire will be exposed to, Its recommended to use thin (~0.25 mm) molybdenum wire, whieh bas both _very high melting point (2896 K), low thermal expansion cnefficiem (4.8 ym" K"), end. does not react with HS, Still certain care should be taken to prevent the exposure of the molybxenum wire oxygen containing mixtures (e.g at) atthe temperatures exceeding ‘700°C because fast oxidation reaction happens at 760°C. Figure 7 shows a schematic of a lissociation reactor with Alternative Current (AC) corona discharge comprising high voltage power supply 21 and conductive wire 22, Very similar raccor is presente in Fig. 9, however Direet Current (DC) power supply in this ease allows charge separation that promotes ionic catalysis,WO 2010141496 PCT/US2010/036941 Anoxher possible plasma souree for low power radical production is glow discharge. Wis organized between high vollage eathode and grounded! anode, which are located on the flanges ofthe reactor tube, Unlike the eonona discharge, there are no strict physical ‘requirements on the enode and cathode materials as they are located outside of the heating, zone, but some non-corrosive metal is recommended (e.g, stainless stel) due to constant exposure ofboth electrodes to HS. The major requirement for glow discharge is low ‘pressure that has to be maintained on the level of 10/Torr or less. Figure 8 shows a schematic, ‘ofa dissociation reactor with glow discharge comprising high volage power supply 31, cathode 32, and anexle 33, tis possible to use other plasma sources, like dielectric barrier discharge, pulsed corona, micro-lischarges, ete, Figure 10 demonstrates the use of low-current arc or tmospherie pressure DC glow discharge (similar to that used in Gliding Are Tornado reactor). Plasma can be generated inside H:S gas, or separately (e.g. discharge in hydrogen ‘or in gaseous sulfur) with further injection into HLS gas. ‘The reactor presented in Fig. 10 is similar to that presented in Fig. 9, however it use DC cischarge combined! with the biased voltage insteal oF corona. In that case ions ‘generated inside the discharge ean promote dissociation outside the discharge zone using ionic catalysis Its possible to combine key features af the disclose! relatively low-teraperature reactors with additional features like product separation, e.g, separating hydrogen and sulfur, using, for example, centrifugal forees (gas or reactor rotation) or elevrical forees (eg, radi clectre field for separation of charge clusters). Also, the prescntly disclosed processes can be realized inside a system with elfective thermal energy recuperation, ¢4, the reverse-vortex reactor. High energy efficiency of HsS dissociation can be accomplished with a GAT reactor, Which is an exemple of «relatively low-temperature reactor with generation of radicals and ions. GAT reactors utlizea sliding are plasma discharge in reverse vortex low, The GAT, like many other plasma discharges, ean be used asa volumetric catalyst in various chemical processes, Some main features that make the GAT attractive are that it ensures uniform gas trestinent and it has rather long residence times. Also the reverse vortex flow creates a low temperature zone near the cylindrica] wall of the reactor and a high temperature zane neat the reactor axis. This, in combination with a centrifugal effec, allows sulfur extraction from theWO 2010141496 PCT/US2010/036941 1 high temperature zone o the low temperature one, As a resul sulfur quenching ean occur 2 within the reactor, Since H.S is quite susceptible to plasma decomposition, GAT is not only 3 avinble method but may also be a cost-effective method for H:S dissociation. Further details 4 ofthe GAT can be found in U.S, Patent Application Publication 20060266637, the contents 5 of which are hereby incorporated by reference in their entirety ‘ Accordingly, provided isa method oF HS dissociation comprising providing a plasma 7 reactor, The plasma reactor comprises a wall defining a reaction chamber: an outlet; 8 reagent inlet uid connected to the reaction chamber for ereoting a vortex flow in the 9 reaction chamber @ first electrode; and a second electrode connested to @ power source for 10 generation of a siding are discharge inthe reaction chamber, The method! furiner comprises 11 introducing HS into the reaction chamber in a manner which ereates a vortex flow in the 12 reaction chamber and dissociating the HeS using a plasin assisted flame. B In the method, the vortex flow can be a reverse vortex flow, which can be create by 14 feeding H,S into the reaction chamber ina direction tangential to the wall ofthe reaction 15 chamber. The plasma reactor ean comprise first andl second ends, the reagent inlet con be 16 located proximate to the Fist end, the eactor can further comprise a Second inlet Auidly 17 connected to the cond end of the reactor, and at leet some ofthe H:S can be provided 10 18 the reaction chamber via the second inlet. The plasma reactor can comprise a movable 19 second electrode and the method ean Further comprise the steps of igniting an electrical are 20 with the movable second electrode in fist position, and moving the movable second eleetrode 1 « second position farther fhom the first elecrode than the fist position for ‘operation ofthe reactor. 2 ‘While various embodiments have been described, itis to be understood that variations 24 and modifications may be resorted to as will be apparent to those skilled inthe art, Such 25 variations and modifications are tobe considered within the purview and scope of the claims 26 appended hereto.WO 2010141496 PCT/US2010/036941 WHAT IS CLAIMED IS: A metliod of HS dissociation comprising generating radicals or ions in a reaction zone and adding H:S 10 the reaction zone to initiate HS dissociation ata temperature of Tess than 1900 K, 2. The method of ela 1, wherein HS dissociation is initiated at a temperature of less than 1875 K. 3. The method of claim 1, wherein HS dissociation is initiated ata temperature of less than 1700 K, 4, The method of claim 1, comprising maintaining a temperature of 800 K 10 1700 K. 10. ‘The method of clamn L, wherein the method comprises a residenoe time of 0.01 10 10 ‘The method of elaim 1, wherein the method comprises a residence time of from 0.1 10 ‘The method of elem L, wherein the radicals or ions comprise H and SH. ‘The method of elaim 1, wherein radicals or ions are generated using corona discharge, ‘The method of clan |, wherein radicals or ions sre generated using glow discharge. ‘The method of claim |, wherein radicals or ions are generated using dielectric barvier lischarge, pulsed corona, or micro-lischarges. un ‘The method of elaim 1, comprising using a gliding are ina tomado reactor,WO 2010141496 PCT/US2010/036941 12, The method! of claim 1, comprising using a low current <5 A are or glow discharge at pressures between 0,0] MPa and | MPa, 13, The methoe! of elaim 1, wherein HaS dissociation results in formation of H:S:, 14, The methodl of claim: 1, wherein a plasma is used to ereate ions 15, The methoe! of elaim 14, wherein the ions are negatively charged sulfur ions. 16, The methoc! of claim 14, wherein a DC glow discharge is combined witha biased voltage to create the ions 17. The methox! of claim 14, wherein the residence time in the reaction ne ranges from about 0.01 1 105. 18, The methocl of claim 17, wherein the residence time in the reaction ne ranges from about 0.01 10 1.08. 19, A metho! oF HES dissociation comprising: providing a plasma reactor, said plasma reactor comprising: ‘wall defining reaction chamber; enoutlet, ‘reagent inl uid connected to the reaction ehamiber for ereating & vortex ‘low in said reaction chamber, a first elevtrode; and 1 second electrode connected to power source for generation ofa sling a discharge in the reaction chamber; introducing H, into said reaction chamber in a manner which creates a vortex flow in the reaction chamber; and dissociating said H,S using «plasma assisted flame to ereate ions, with the dissociation being initiated at a temperature of les than 1900 K.WO 2010141496 PCT/US2010/036941 20, The method oF ela 19, wherein the residence time inthe reaetion chainber for lissociation ranges from about 0.01 10 10's, 21, The method of elaim 20 wherein the residence time in the eaetion chamber for dissociation ranges from sbout 0.1 10.0, 22, The plasma reactor of claim 19, wherein said vortex flow isa reverse vortex flow. 23, The method of elaim 22, wherein said reverse vortex flow is created by Feeding HS. imo said reaction chamber in a direction tangential to the wall of said reaction chamber. 24, The method of claim 23, wherein ssid plasina reactor comprises first and sevond ends, ‘the reagent inlet i located proximate tothe fist end, the eactor further comprises a second inlet fluidly connected to the sevond end of said reactor, and wherein atleast some of said HS is provided to the reaction chamber via the second inlet 25. The method of elaim 24, wherein the plasma reactor comprises a movable second electri and said method! further comprises the steps of igniting an electrical arc with said ‘movable sovond electrode in a first post eand electrode to 8 on, and moving the movable second position farther from said first electrode than said frst position for operation of saidWo 2010/141496 t 0.00 2 2 2 2 2 2 S a S B eS 5 © + + ° o a (‘jowsaa) ysog ABseug SUBSTITUTE SHEET (RULE 26) PCT/US2O10036941 - - 1 4.50 2.00 2.50 3.00 Energy Input (eV/mol.) 1.00 T 0.50 2° S a FIG. 1PCT/US2010036941 WO 2010/141496 2/16 old SUBSTITUTE SHEET (RULE 26)PCT/US2010036941 WO 2010/141496 3/6 € Old (y) eanjesedwiay 0091 O0St OO O0€! O0ZE O0lL 0001 006 008 ee eee peg eee ogee 00'0 oro 0z'0 TP tce seco song, on ae or'0 ° *. 6 0s°0 a ary 09°0 ee. ° we ° 020 OUU8Y | ZH® lay . : soneuly ZH o ce, . 080 owueyL SZH* fee, 06'0 soneuly SZH © eee ood uonoeiy sseW SUBSTITUTE SHEET (RULE 26)WO 2010/141496 PCT/US2010036941 416 £ = 2 Q = ao S 3 wh 2 € 5 g 2 = L& ni 2s 5 3 ao 3 bS a a3 £ > o ee L838 “2 £ > > 5 sf Low 2 + 3 S ms) ° Q °Q 2 ° 2 2° 8 ina oS Seo. se 8 © a) a = = 3 3 (you/Aa) 3805 ABseug SUBSTITUTE SHEET (RULE 26) FIG. 4WO 2010/141496 HS: 12 HS FIG. 6 RSS PCT/US2010036941 Products —— SSS 32 33-> Bie] FIG. 8 SUBSTITUTE SHEET (RULE 26) | Products: _WO 2010/141496 PCT/US2010036941 Furnace Corona wire FIG. 9 SUBSTITUTE SHEET (RULE 26)