“USO05674377A United States Patent 5 11) Patent Number: 5,674,377 Sullivan, IIT et al. (45) Date of Patent: Oct. 7, 1997 [54] METHOD OF TREATING SOUR GAS AND peated fanaa ae 7 nee LIQUID HYDROCARBON (SSL 121986 Jone 38 a 4,710,305 12/1987 AllisOM ...oncnon 210747 [75] Inventors: Daniel S. Sullivan, I; Allan R. ee oa a ee 4778609 10/1988 Kochet a ams : Gi . 4952 t2190 Dion fname Taylor; Paul Yon-Hin, both of 5,128,049 7/1992 Callin Be sam amb nel eoncetatons were detmined er ten to Las ‘ment. Samples were then treated with 60 ppm chemical (Cexthnay ca additive to reduce the HS concentrations in the vapor sp espace Rena ep in TABLE W. Sch tase ame ‘hydro 1,3,5- PLABLEIEVS cans ea 6c Re amma ral me bygo-.s 2s prs e Se soe Eee 2 ct taunt ago ase nn er: a ne a cee & 8 8 The TABLE data reveal he 13.6texahyeo13. (ertbuy) tain tbe te mot eecve savage sed < a i 7 Series IV Tests: Its significant to note thatthe tert-butyltriazines (Samples ‘Aand B) were much more effective than the n-butyl triazines and the sec-butyltriazines (Samples C-1 and C-2), Series Tests: Aliquots of $00 ml each of a No. 6 fuel oil from a U.S. tion ‘West Coast refinery were tested to determine the ab capacity of the tertiary butyltriazine relative to the abi several Scavengers to reduce H,S vapor headspace concen- trations. The Samples used in the experiments are identified on TABLE I. When possible, sour hydrocarbon samples were heated to simulate system temperatures. Vapor head- space concentrations were determined prior to treatment using Drager detector tubes. Samples were then dosed with 216 ppm (actives) of an H,S abatement chemical additive using an eppendorf pipette, sealed in the container, shaken, and placed in a 130° (64.4° C.) water bath fortwo hours. One container served as a blank. Reductions in vapor headspace HS concentra- tions were then determined after the heating cycle using fresh Drager detector tubes. Results ae reported in TABLE mL. ‘TABLE 1 —Hicsarmce 28 (op) ital Final Amo HS Sumple HS Conc. HS Cou. Consaned "Bink 00 Ts “315 Gun) a 580 ‘2s 2s es 70 ns 5 er 7s 00 +125 xin) oy 350 as 22s 45 0 5s 6 In these experiments, two sour distillate streams and a light cycle oil (LCO) from a Canadian refiner were used t© determine the effectiveness of the tertiary butyltriazine. ‘Historically, distillate streams 1 and 2 including LCO are difficult to treat due to reactive species competing for the HS scavenger. Consequently, high dosages were required to reduce the H,S concentrations in the vapor space, ‘The same procedure was followed as used in the Series I ‘Tests, except that a one hour heating cycle at 100° F. (37.7° C.) was used for distillate steams I and 2. A two hour heating cycle was used during the evaluation of the LCO. ‘The streams were treated at three different dosages com- ‘monly utilized by the refiner, Results are reported in TABLE, v. ‘TABLE V —__Heaissce H.S (oom Dose Init! ial Amount (enn) SHS HS Sample Steam (Actives) Cone. Cone. _Conumed Bik 7 py sm 2 (os) A 1 4% BO 3 eu 1 pa % 5 (win) er 1 % nD 3 Gia) eo 1 PH nu 4 7 Blank 2 0 Bu 4 (os) a 2 3 0 3 cu 2 50 Oo 2% uM co 2 90 * 35 co 2 5 2 1 2 Disk = «co m9 '5 (os) ‘ too m0 cn eo 2s as 05,674,377 7 TABLE V-continued Headspace HS (oom) Dosage Inal aal—Aroune fom) SHS HS Suaple Steam (Aaiet) Coss, Conc. Consumed a ro 2S ~o co ico 2 8 Series V Tests: In this experiment, the same general procedure as used in the previous tests were employed, except sour FCC Cat Slurry Oil (CSO) was treated with chemical additives at 30 ppm (Actives). Produced FCC CSO, obtained from a Northeastern Refiner, is typically tteated before going to tankage. The samples were heated to 190° F. (87.7° C.) and held at that temperature for two and ‘a half hours. Results are reported in TABLE VI. TABLE VI Hespice HS (os hia Fos Amount H,S Sample __H,S Cone, HS Conc, __Consuned ‘Bink Fry 75 25 (los) a 5 40 135 ce us % 2 cr 135, ® 7 6 170 8 0 ‘The Series Il, I, IV, and V Tests demonstrate the effec- tiveness of the 13,S-hexahydro-1,3,5-tert-butyltriazines over other commercial scavengers under a varicty of treating conditions and concent several different hydrocarbons, including crude oil, refined oil, CSO, BTHGO, and LCO were used in the comparative tests. A ‘particular advantageous feature of the scavenger used in the 1s 2s 8 ‘method of the present invention sits fast reaction with the HS. The Series IL IM, and IV Tests demonstrated effective scavenging within 1.2, and 2.5 hours. An important property of the Seavenger used in the present invention isits solubility in oll, hich permits it to rapidly disperse inthe sour ols. What is claimed is 1. Amethod of reducing H,S in a hydrocarbon fluid which comprises contacting the fuid with an effective amount of a 13.S-hexahyéro-13.5tert-butyl triazine, the concentration of the 13.S-hexahydro-1.3 Stert-butyl wiazine inthe uid ranging from 50 t0 3,000 ppm. 2. The method of claim 1 wherein the fluid is a gas or oil and the compound is introduced therein in an amount equal to I to 50 pounds of the triazine per pound of HS removed. 3. The method of claim 1 wherein the Buid is gas stream or an oil steam. 4. The method of claim 1 wherein the triazine is intro- duced in neat form. ‘3. The method of claim 1 wherein the triazine is intro- duced int the hydrocarbon fluid with a hydrocarbon solvent or diluent. 6. The method of claim 1 wherein the concentration ofthe Iciazine in the fluid ranges ftom 50 to 1,000 ppm. 7.Amethod of reducing H,S in a hydzocarbon fluid which ‘comprises introducing into the fui a scavenging amount of, a scavenger formulation comprising (@) from 5 t0 95 wt % of 13.S-hexahydro-13,5-tert- ‘butyltiazine, and (©) from 95 t0 5 we % of a diluent or solvent for the triazine, 8.'The method of claim 7 wherein the hydrocarbon fluid isan oil stream. 9."The method of claim 7 wherein the triazine comprises from 20 to 80 wt % of the formulation