6, os) wy ey co) 6 (2) (8) 66) United States Patent Swallow et al. METHOD AND APPARATUS FOR ANALYZING ACID GAS LOADING WITHIN ‘AN AMINE SOLUTION Inventors: Jamie Swallow, High River (CA); Brent Richmond Young, Calgary (CA) Assignee: Spartan Controls Ltd., Caleary (CA) Notice: Subject to any disclaimer, the tem ofthis pateat is extended or adjusted under 35 USCC. 154(b) by 226 days. Appl. No. 09/919,331 Filed: Jul, 30, 2001 Prior Publication Data ‘us 20nsm22366 AI Jan. 30,2005, Int. C7 GOIN 3300 US. cL 436/121; 43661; 436/100; "436/133; 436/149, 436/150; 436/178; 422/82.015, 422082.02 Fleld of Search 436/121, 61, 100, 436/133, 149, 150, 178, 11-112, $5, 163, 120, 139, 102; 422/82.02, 68.1, 80, 75, 16, 77, 428229, 226, 228 References Cited US. PATENT DOCUMENTS. ‘US006767746B2 (a0) Patent No. US 6,767,746 B2 5) Date of Patent Jul. 27, 2004 4705508 A+ 1989 Yon 210609 ASOUSSL A > L108 Bye eal aon sant A + Mom Bye ‘3010 Sooss A + in902 Comings ea Babee Saoaatr A + 'xi904 Koy etal dst Sage A allo Cummings eal. 42202 Shiva A + loin tchunanetal 2 @aaat0 Sous? A + MIG) Rodrigues eta oc 468 Gontasa A + eco Dingman de C2828 BL > 2001 Geo fe eSizjm m+ Baan Rywevakl * cited by examiner Primary Esaminer—ill Warden “Assistant Exaniner—Sam P. Sietke (74) Attorney, Agent, or Firm—obn Russell Uren on ABSTRACT ethos und apparatus used to calculate the bydagen sulfide and carbon dioxide loading of both rich and lean amine Solutions used to remove acidic gas components from sour ‘or prochction gases in order to produce a Sweet or sales for transmission purposes. The amine solution is divided nto three (3) liguid streams eatrying diferent proportions of heat stale salts, hydrogen sulfide and carhon dioxide. Conuetivty measurements ate made on each ofthe steams and are converted to acid loading values for the amine. The acid loading values of the amine are used to obtain the bbydeogen sulle and carbon dioxide loading for the amine solution. 441380 4 + 91978 Atwood sessman 7 Claims, 2 Drawing Sheets hot REGENERATOR/ ABSORBER EGENERAT we) Ho We 1a EB, May HS Bs et 130, wea? > on ac “21 excnanse [7 Feeoien 122 3U.S. Patent Jul. 27, 2004 Sheet 1 of 2 US 6,767,746 B2 SWEET GAS OUT ABSORPTION REGENERATOR/ SoweR | 222 UO | REBOILER FIG. | prior art REGENERATOR/ cee REBOILERU.S. Patent Jul. 27, 2004 Sheet 2 of 2 US 6,767,746 B2 —————— S32 LiquID HgS/COg w/ HSS FIG. 3A CONDUCTIVITY LIQUID HS /COp w/o HSS FIG. 3B CONDUCTIVITY Liquio C02 FIG. 3US 6,767,746 B2 1 METHOD AND APPARATUS FOR ANALYZING ACID GAS LOADING WITHIN ‘AN AMINE SOLUTION INTRODUCTION This invention relates to acid gas loading within an amine solution and, more particularly, to determining hydcoge sulfide (H2S) and carbon dioxide (CO2) loading within the amine solution by utilising liquid conductivity to determine the loading ofthe hydrogen sulfide and carbon dioxide BACKGROUND OF THE INVENTION Contracts are entered between the sellers or producers of natural gas and the transmission companies who transport ‘sich gas within their pipelines, These contracts specify the parameters of the gas sold by the producers that will be transported within the pipelines ofthe transmission compa nies The prices for transportation of such gases arc based on the specifications and, indeed, the gas eventually transported within the pipeline is required t Fall witha appropriate limit parameters. ‘Sweet or sales gas is curried by the pipelines. This yas is the originally produced sour gas which has had a certain perevatage of hydrogen sulfide and carbon dioxide removed. ‘The sour pas emanates from the producing formation of the ci or gas well. It'is transported to an absorber containing an famine solution, The acid gases chemically react with the ye and are removed in their Liguid form. This socalled “sweet gas” from the absorber is subsequently debydrated and sold tothe transmission company ‘The hyelrogen sulfide and carbon dioxide removed from the sour gas leave the absorber within a “rich” amine solution which basa relatively high concentration of the acid hydrogen sulfide and carbon dioxide, This rch amine solu- tion i iniroduced inio a regeneralor or siripper and a reboiler.Asthe rch amine flows through the regenerator and reboiler, the hydrogen sulfide and carbon dioxide is seipped from the amine, The resulting “lean” amine containing relatively low concentrations of hydrogen sulfide and carbon dioxide is recirculated back into the absorber where itis, reused on the sour gis lowing into the absorber as just described, A parameter tat is important for conteolling the revers= ‘ble reaction both in the absorber or contactor and the ‘tipper or regenerator isthe concentration measurement oF the “loading” of the hydrogen sulfide and carbon dioxide in both the lean and ric amine solutions In expect of the lea amine loading calculation, 2 feed forward indication is provided to the absorber which is used to calculate the ‘quantity of lean amine solution which must be provided to the absorber so the appropriate quantity of acid gas is removed from the sour natal gas and lo ensure the sweet ‘or sales gas meets the pipeline specifications. Lean amine ‘calculations furlher provide a feed back indication of how ‘efficiently the eezeneratoris stripping the acid eas from the rich amine liquid, In respect of rich amine liguid, a Teed forwatd indication forthe calculation is provided which will provide the quantity of energy necessary within the Fegenetatorteboiler to strip the acid gas from the rich amine liquid Heretofore, the measurement for amine loading of the amine solution used to remove the acid gases from the production sour gas was obtained by diving the acid gas ‘Components af the liquid amine into the gascous phase and then analysing the eises. An ultraviolet gas analyzer was % o 2 used for the hydrogen sulfide and an infrared analyser was used forthe carbon dioxide, The results ofthe wo analyzers were expressed as a concentration measurement, coave- neatly paris per million (ppm or grains gallon ‘While this technique has certain advantages such as ‘confining the concentration measucements 10 the wo spe- tific gases, namely carbon dioxide and hydrogen sulfide, and thereby avoiding interference with anyother gases in the gas stream, the use of two analyzers is expensive, ther is large lag time to obtain the measurement because of the phase cchinge requirement and the maintenance costs for ‘wo analyzers and their associated components ate high SUMMARY OF THE INVENTION According to one aspect of the invention, there is pro- vided a method for determining the acid concentration of an mine solution eieying bydragen sulfide ad carbon dioxide ‘comprising the steps of determining the conductivity of a lint liguid stream containing said hydrogen sulfide, said carbon dioxide and heat stable salts in said amine solution; removing significantly all of said heat sable salts from said fist Tiguid stream to form a second liquid stream; determin- ‘ng the conductivity of said second liquid stream containing sad hydrogen sulfide ad sail carbon dioxide without said bit stable salts; removing significantly all f said hydrogen sulfide from sic second ligucl sieam to form a tint liquid steam; determining the conductivity of said tied liquid ‘ream containing said carbon dioxide without said hydko- en sullide; and snalysing said conductivity measurements ff said fist, second and thied Tiquid streams to obtain said acid gs loading of said amine solution, According to a further aspect of the invention, there is provided, apparatus for determining the acid concentration ‘of an amine solution carcying hydrogen sulfide and carbon dioxide comprising a first analytical eell for measuring the conductivity ofa first liquid stam containing said hydeo- ‘gen sulide, said carbon dioxide and heat stable mals within Said amine solution, a second analytical cell for measuring the conductivity of said second liqu stream containing said hydrogen sulfide and carbon dioxide without sid heat stable salts, a hydrogen sulfide remover for acing on said second liquid stream and removing suid hydrogen sulfide thereby 10 orm a thied liquid siram, «third analytical cell for mea- suring the conductivity of said third Liguid stream containing sad carbon dioxide without said hydrogen sulfide and ssid beat stable slls and a computing device operable to receive signals from said frst, second and thin analytical eels, 10 analyse said measurements of said conductivity of said fst, second and third analytical cells and to produce a value for Said eid concentration of said amine solution, BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS Specific embodiments of the iavention will now be described, by way of example ony, with the use of drawings in whict FIG, 1 illustrates the eemoval of acid gases from sour gas {nan absorption ower and the recirculation of lean amine to the absorption tower according to the PRIOR ART; FIG. 2 illusrates the measurement of conlutivity of 3 first, second and thied liquid steeam carrying hydrogen salide and earbon dioxide according to the invention; and FIGS, 3A, 3B and 3C illustrate the conductivity measure meals for each ofthe first, second and third liquid steams, according to the invention,US 6,767,746 B2 7 DESCRIPTION OF SPECIFIC EMBODIMENT. Referring now to the drawings, the apparatus used gen- ally forthe removal ofthe acidic gas components of a sour fs production flow and the recirculation of unine according {0 the prior ar i shown generally at 100 in FIG. 1. The production or sour gas 101 is flowed info an absorption tower 102 carrying an amine solution. ‘The acidic gas ‘components, principally hydrogen sulfide (H25) andl carbon. ‘dioxide (CO2), react with the amine solution and ener into the solution thereby creating « “rich” amine soltion with high concentrations of hydrogen sullide and earbon dioxide, Which rich amine leaves the absorption tower 102 at 103 “Sweet” of sales gas without the aeidic components leaves, the absorption tower 102 at line 104, The sweet gas is dehydrated and sold to a transmission company for tans portation to markets, “The rich amine solution ia line 103 is introduced to a regeneratortehoiler 110. The hydeogen sulfide and carbon ‘ioxide are “stripped!” from the amine asthe solution flows, downwardly within the regenerator/eboiler 110. and the “lean” amine without significant concentration of hydrogen, sulfide and carbon dioxide leaves the regenerator reboier 110 at IIL and is reintroduced into absorption tower 102 through line 112. The technique described is commonly used in the PRIOR ART and forms no part of the present Inorder to obtain the necessary quantity of ean amine for tse in the absomption lower 112, the hyeiogen sulfide and ‘carbon dioxide concentration or “loading” of the amine Solution is required for both the rich amine leaving absorp- tion fower 112 and the lean amine being reintroduced into absorption tower 102 Irom reyeneratorireboiler 110. These figures are required for several purposes, Firs, the eoncen- tration i required so as to provide an indication of the ‘quantity of Team amine solution that must be eieulated into the absorption tower 102 to remove the necessary acid ‘components from the sour gas of the production well so as to meet pipeline specifications and trinsmission contracts. ‘Second, the concentration ofthe lean amine gives an indi ‘ation of the operating eliceacy of the regeneratorireboiler 110 in removing the acid gas components from the rich amine solution. Third, the concentration of acidic compo- nents in the rich amine solution provides a feed forward indication of the energy that will be required within the regeneratorteboiler 10 to strip the acid gases from the rie Reference is now made to FIG. 2 whic illustrates the ‘method and apparatus eonvenicatly used according t0 the Jnvention. The process of FIG. 1 eootinues; that i te ri famine leaves the absorption tower 102 at 103 and is directed to the regeneratorlehoiler 110 where the hydrogen sulfide tnd carbon dioxide components are removed and the lesa 1 exiting from the regeneratorteboiler 110 is eintro- ‘duced into absorber 102 at L12 as has been described, However, a further liquid stream 113 is created which uses the sich amine leaving the absorption tower 102 and withia whieh tbe degradation product of heat stable salts (HSS) are of interest Liquid steam 113 is conveniently divided, for description purpeses, into thee different streams, namely first liquid ‘team L14 extending from absorption rower 102 to a heat Stabe salt remover 122, conveniently an on exchange bed, second liquid stream 120 which extends from the ion ‘exchange bed 122 to reboiler 128 wherein the hydrogen ‘sulfide is removed from the rich amine and thind quid Stream 121 which carries the amine solution now only with the carbon dioxide acid gas components. % o 4 Three (3) analytical cells 124, 130, 131 are provided for measuring the conductivity of each ofthe fist, second and ‘ied liquid streams 114, 120, 121, respectively: that is, the ccondictivty of the rich amine containing the heat stable salts, the hydrogen sulfide and the carbon dioxide is mea- sure by first analytical cell 124; the condhitivity ofthe rich Amine withthe heat stable salts removed and thereby form- jing the second liquid stream 120 is measured at second analytical cell 130; and the conductivity of the rich amine ‘with the heat stable sal and the hydrogen sulfide removed and thereby forming the third guid steam 121 i measured third analytical cell 131. These conductivity measure- ‘menis are used to determine the rich and lean amine losding 8 will bo described. Operation In operation, the conductivity measurements taken a each of the analytical cells 124,130, 131 will be used to caleulate ine lean and rich amine loading and reference therein is now ade fo FIGS. 34-3, a general, the slope of the line 132 known forall ofthe fist, Seon snd third guid siceams 114, 120, 121; that is, as the concentration of the conductive eat stable sills, ceabon dioxide and hydrogen sulfide within the amine increases, the conductivity will also increase and the posi- tioning and slope of line 132 is obtained by iterative graph- ing prior to the conductivity calculations so thatthe line 132 {sina kaowa position onthe three graphs illustrated. A first conductivity measurement, CF, is obtained from first ana- lytical cell 124 for the first liquid streum 114. By contact ‘it slope 132 t0 obtain an appropriate ordinate value, a figure C1 is obtained for the loading of first liguid stream U4 whieh is carrying the hydrogen sulide, the eabon dioxide and the heat stable sais. Likewise, the second conductivity measurement, C2’, is obtained from second ‘analytical cell 130on the liquid steam 120 in which the heat Stable salts have been removed by ion exchange bed 122 Te second conductivity measurement will give a figure C2, Jor the loading of the second liguid steeam 120 but which liguid stream has the heat stable salts removed. Similarly, 2 thitd conductivity measurements C3' is obtained for the loading ofthe third liquid siecam 121 by third analytical cell 131 and, by similar technique, a value C3 is obtained for the loading ofthe tied liquid stream 121 but which stream ony cates carbon dioxide in the amine, the hydrogen sulfide hhaving been substantially removed by passing the solution ‘through reboiler 123 where the hydrogen sulide is stripped from the amine and vented from reboilr 123, By utilising the figures C1, C2 and C3, the hydrogen sullde was loading may be obtained as follows: “Tow aid ps esingct-c2 o aon dnd ong 8 @ tf ogni dinge(1-C2)-C2 @ i can therefore be seen that the use of conductivity ‘measurements as takea on three different liguid streams will give the loading quantities of the carbon dioxide and hydo- {gen sulfide components of an amine solution which is usefl Tor processing purposes in progucing the sweet or sales gas from production of sour gas in the liquid phase therchy removing the necessity of converting the liquid components fof acid gases tothe gaseous phise which reduces response time. ICs also beneficial that gis analyzers with theieUS 6,767,746 B2 5 ‘concomitant maintenance requirements are not necessary and the calculation ofthe factors C1, C2 and C3 from the ‘conductivity measurements are obtained throvgh well, proven technology in other liquid analytical applications. ‘While the ealeulation of the amine loading has been given ‘with respect to graphical techniques which are caried ot ‘manvally according t0 the invention, iis, of course, quite ‘lea thal the values could be obtained by way of appropriate transducers of ater sensors which provide information 10 & ‘computing device, a controller andor an associated micro- processor or tbe lke thereby allowing an automatic ealeu- lation of the conductivities andthe acid gas loading which ‘ean also be used to adjust te processing parameters used to ‘trip the rich amine and thereby form the lean amine for recitculation. Further, while the invention has been specifically described 4s being particulacy applicable 10 analysis of a rich amine solution, iti likewise applicable to lean amine solutions ‘Many modifications will eadily occur to those skilled in the ant to which the invention relates and the specific ‘embosliments described should be tke as illustrative ofthe {vention only and aot as limiting its scope as defined in accordance with the accompanying claims. We elim: 1. Method for determining the acid concentration of a amine solution carrying hydrogen sulfide and earbon dioxide received from sour gas comprising the steps of detemining the conductivity of a fist liquid stream containing. said hydrogen sid, said carbon dioxide and heat stable sats in said amine solution; removing significantly all of said heat Stable salts from said first liquid stream t0 form a second, id seam; determining the conductivity of said second liguid steam containing said hydrogen sultide and said cearbon dioxide without said beat stable salts; removing significantly all of said hydrogen sulfide from suid second Tiguid stream to forma third liquid streams determining the 6 conductivity of said third liguid stream containing. said carbon dioxide without sad hydrogen sulfide and said heat Sable salis; and snalysing said conductivity measurements of std first second and thed liquid streams to obtain said acid gs loading of said amine solution, 2. Method as in claim I wherein sad amine solution is 3 rich amine solution, '3. Method as in claim 1 wherein sa Jean amine solution, 4 Apparatus for determining the acid concentration of mine solution earrying hydrogen sulfide and carbon dioxide received from sour gas comprising a fist analytical cll for ‘measuring the conductivity ofa fist liquid stream contain- ing said hydrogen sulfide, said carbon dioxide and heat lable salts within said amine solution, a second analytical xl for measuring the conductivity of said second liquid Seam containing sal hydrogen sulfide and said carbon dioxide without ssid heat stable salts, a hydrogen sullide remover for acting om said second liquid stream and remov- ing said hydrogen sulfide thereby to form a thied liguid steam, a third analytical cell for measuring the conductivity ‘of said third Tiguid stream containing said carbon dioxide ‘without said hycrogen sulfide and said heat stable salts and computing deviee operable 10 reecive signals from said fir, second and third analytical cells, to analyse. seid ‘measurements of said conductivity of sid fist, second and third analytical cells andl to proskice a value for said acid ceoncenttalion of said amine solution ‘3. Apparatus as in claim 4 wherein suid beat stable salt remover is an ion exchange bed ‘6. Apparals 3s in claim $ whercin suid hydrogen sulide remover is 4 reboiler "7 Apparatus ai claim 6 wherein sad computing device isa controller or 8 microprocessor. amine solution is 3