(2) 6 03) om en @ 6s) oy 2) 658) 66) United States Patent Salma et al. FAST, HIGH CAPACITY HYDROGEN SULFIDE SCAVENGERS Inveators: Tauseef Salma, Sugar Land, TX (US) Alexander A. Lambert, IIT, Houston, TX (US); Gordon T. Rivers, Houston, 1X (US) Assignee: Baker Hughes Incorporated, Houston, 1X US) Notice: Subject to any disclaimer, the team ofthis pateat is extended or adjusted under 35 USC. 1540) by 47 days. Appl. Now 11/514,594 Filed: Sep. 1,2006 Prior Publication Data S 2008/0056974.A1 Mar. 6, 2008 InCl. CORE 168 (200601) c10G 2920 (200601) us.cl. 428/220; 423/242.7; 48/1273; 48/127 5; 208/14; 208/208 R; 208/236 210774; 210/750, 210916 Field of Classification Search 48/1273, '48/127.5; 208/14, 208 R, 236; 2107749, 210/750, 916; 252/189, 190; 423/220, 242.7; S441, 180 Se application file for complete search history. References Cited US. PATENT DOCUMENTS 2406596 A 21950 Moyer etal divas A $1982 Moyers Bsvm425 A 51952. Moyer. 2729679 A V/19S6 Anderson fois A 21974 Borehen 1,8 Mas pte Maes Scavenger ‘US007438877B2 (10) Patent No. 4s) Date of Patent: US 7,438,877 B2 Oct. 21, 2008 4978512 8121990 Dion Suro A 71902 Gatlin S3ia6n A S904 Vasil, SaSKI A 11990 Gatlin E5549 A 911990 Rivers etal SGMA7T A * 10199? Silvan ea Soot A 121991 Truler etal 5744024 841998 Silvan, IL 5058352 A 911999 Callaway ea 65.624 BE 62003 “Tite eal, BesnSit B2* 122003 Salmactal 200510238586 1 102008 Pakulki eal PORPIGN PATENT DOCUMENTS on oxo Gn 2200812 A * (OTHER PUBLICATIONS ea) 11956 Jan M Bakke ot sl. “Hydrogen Sulfide Scavenging by 135 Thazinanes, Comparison ofthe Rates of Reaction In. Eg. Chen Res, vol 43, No.9 (2008), pp, 1962-1965 LE. Walker, Fonmalchyd, 1064, pp. 360-361, 610, 613, Reinhold Now York * cited by examiner Timothy C Vanoy Madan Mossman & Sriram Primary Examiner (14) Attorney, Agen, or Firm Pc on ABSTRACT Selective, imeversible removal of hydrogen sulfide (1,S).and ‘ther sulfiydry] compounds from a gas steam, such as sour ‘natural gas and sour hydrocarbon liquids is achieved with a seavenging agent having hydroxyalkyl funetionality and alkylamine functionality. This seavenger possesses «higher ‘capacity for FS removal compared with a seavenger having only hydroxyalkyl functionality. The seavenging agent is ‘made by reacting at least one alkanolamine and at least one alkyl amine with an aldehyde, sch as formaldehyde 24 Claims, 1 Drawing Sheet eacton Tima (mi)U.S. Patent Oct. 21, 2008 US 7,438,877 B2 © Composition A | Hsw700 H,S Mass Uptake/ Mass Scavenger o 4° 8 2 1% 2% 2 8 a Reaction Time (min) FIG. 1US 7,438,877 B2 1 FAST, HIGH CAPACITY HYDROGEN SULFIDE SCAVENGERS ‘TECHNICAL FIFLD ‘The invention relates to chemical compositions and meth= ‘xs for scavenging sulfhydryl compounds, particularly hydrogen sulfide (H,S), Irom “sour” aqueous and hydroear- bon substrates, and more particularly relates, in one non- limiting embodiment, to methods and compositions useful as scavengers 10 remove sullhydryl compounds from natural as. BACKGROUND “The removal of H,S and other sulfhydey compounds ftom 8 liquid or gaseous hydrocarbon stream is a problem that has challenged many workers in many industries. One sich industry is the petroleum industry, where the HS content of ‘erin eres fom reservoirs in toohigh for commercial acceptance. The same tre of many natural gas steams, Bven where a eride or gas seam con ‘wins only a minor amount of sulfur. dhe processes to which the crude il or fractions thereof are subjected often produce ‘one or more hydrocarbon streams that contains H,S. ‘The presence of 11,5 in hydrocarbon streams presents ‘many environmental and safety concerns. Hydrogen sulfide is highly flammable, toxie when inhaled, and strongly irritates the eyes and other mucous membranes. In addition, sul ‘containing sls ean deposit in and plug or corrode tansiis= son pipes, valves regulators, and he like. Flaring of natural tas that contains H,S does not solve the problem for gas ‘reums because, unless the HS is removed prior o Marin, the combustion products will ontain unacceptable amounts ‘of pollutants, such as sulfur dioxide (S0,)—a component of “acid rain.” Hydrogen sulfide has an offensive odor, and natural gas ‘containing H.S often is called “sour” gas. Treatments 10 reduce or remove H.S from hydrocarbon or other substrates often ate called “sweetening” treatments. The agent that is used to remove or reduce HS levels sometimes is called @ “scavenging agent” or “scavenger” The swostening or scav~ ‘enging of HS from petroleum or natural gas is only one ‘example of where [1,8 level reduction or emoval must be performed. Many aqueous substrates also must be trated 0 reduce or remove HS. In the manifactured gas industry, or the eoke-making industry, dhe destructive distillation of bituminous eval witha high sulfur eontent commonly produces coal gas contining ‘anunacceptable amount of HS. Another HS contamination problem arises during the manufacture of water gas or sya- thesis gas. Water gas or synthesis pas streams that conti H, Soften are produced by passing seam over bed ofincan- descent coke of coal, The incandescent coke of coal often ‘contains minor amount of sulfur, which contaminates the resulting gas stream, ‘The problem of removing or reducing HS from hydrvcar- bbonand aqueous substeates has boon solved in many diferent ways in the past, Most ofthe known techniques involve either {.)absorption, orseletiveabsomption by suitable absorbent, alter which the absorbent is separated ad the sulfur removed to regenerate and reeyele the absorbent, or () selective rene- tion with a reagent that produces a reaiy soluble prodct. A numberof knovin systems tata hydrocarbon steam with an ‘amine, an aklehyde, an aleohol, and/or a reaction product thereat. The wide variety of processes, patents tions that describe a nany ares of the Word is 2 o 2 carbon steams is evidence that itis desirable and necessary to remove H,S from aqueous ad hydrocarbon streams. 'A continuing need exists for aliemative processes and compositions reduce andlor remove H.S fromaqueous and hydrocarbon substrates, The need for removing sullhydry] ‘compounds from hydrocarbon substrates has increased asthe world's supply of “sweet” natural gas and eride oil is reduced. would ths be desirable to discover andior develop few scavenging agents that ae fst and have a high capacity {orsemoving sulfhydryl compounds compared with known scavengers, SUMMARY, ‘There is provided. in one form, « method for reducing the ‘amount of sulfhydryl compounds in sour aqueous and sour hhydrocarbon substrates that involves scavenging the sultby- i] compos rom the arate wh avenging get ‘contsns a triazine which has both hyoxyalky! and alylaminefanctnaliy. The seavenping ses present in ‘an amount suficent to reduce said amount of sai sulfiydry ‘compounds in said substrate ‘There is further provid in another non-limiting embodi- ‘meat a method for reducing an amount of sulthydryl com- pounds in sour hydrocarbon gas that concen seavenging the sulthydryl compounds from the gas with a teiazine seaveng- ing agent. The agent is present in an amount ranging from about 0.00045 to about 134 gallons per ppm of sullhydryl ‘compous to be removedxMMsef of gas (0.06 0 1790 liters scavenger used/(ppm sulfhydryl compound removedx ‘MMsem), where the tz has te sructre: Cy rN In structure (I) the R groups are independently selected from the group consisting of C.-C, straight or branched alkyl _groups.or ROH, where R, isa CC straight or branched alkylene group, At least one R group is C,-Cay staight or branched alkyl groups and at least one R group is —R, OH. There is additionally provided in another non-restrctive version a substrate trated for atleast one sulthydrycom- potind. The treated substrate may hea sour aqucns substrate, 8 sour hydrocarbon substrate ora mixture thereof. The sub- strate further contains at least one sulfaydey compound and a scavenging agent that includes a tiazine which has both hydroxyalkyl and alkylamine functionality, The seavenging ‘agen is present i an amount sufieient o reduce the amount of the sblfhydyl compounds in the substrate as compared ‘with the sume substrate absent the scavenging agent. FFunber there is provided a sour hydrocarbon gas that is treated for at least one sulfhydryl compound, where the includes atrazine seavenging agent in an amount of fr shout 0.00045 to about 13.4 gallons per ppm of sulfaydry] ‘compound tobe remavesixMMsef of gas (about 0.060 abt 1700 liters scavenger used(ppm sulfhydryl compound semovedxMMsem)) The triazine has the structure (1) aboveUS 7,438,877 B2 3 BRIBE DESCRIPTION OF THE DRAWINGS. FIG. 1 isagraphofthe mtioof HS massuptaketothemass ‘of scavenger as a funetion of time fora triazine ofthe iawen= ‘ion (Composition A) compared oa comparative, monoetha- nolamine triazine (HSW700) having no alkykaminefanetion- aly, DETAILED DESCRIPTION thas been discovered that triazine compounds having at Feast one hydroxyl finetionality, such asa hydroxyalkyl, and at Teast onealkylamine functionality permit selective removal ‘of sullhydyl compounds, particularly HS, fom a gas oF liquid containing the same rapidly and with high capacity. By “seletively” is meant that the sulfhydryl compound is removed relatively faster and in greater proportion compared to another compound present in the gas or liquid, particlariy ‘carbon dioxide (CO,). These compounds are expected 10 imreversibly remove H,S from sou liguidor gas hydrocarbon streams ‘The seavenging agents ofthe present methods and compo= sitions may be used to treat agucous and bytdrocarbon sib- strates that are rendered “sour” by the presence of sulfhydryl ‘compounds, such as hydrogen sulfide (HS), organosulfur ‘componnls having a sulfhydryl (—SH) group, known as mereapians, also known a thiols (RSH, where R is @ hydrocarbon group, thiol carboxylic acids (RCO SH), y straight or brane alky- Tene group, provided thet at least one R group is Cy-Cay sight or brnched alkyl groups and at lost one R group is “ROHL 23, The sour hydrocarbon gas of claim 22 where in the triazine a feast one R group is ROH where Ry is Cz alkylene, and where a least one R group is methyl 24. The sour hydrocarbon gas of laim 22 where the sour hydrocarbon gs is natural gas and at [east one ofthe sulfhy~ dy] compousds is hydrogen sulfide