IP Library › Granted Patent US 12,669,494
Granted Patent B2
US 12,669,494 · App. 18/060,838 · Granted Jun 30, 2026

Sulfur and amorphous dithiazine measurement

Inventor: Jay Locklear (Houston, TX)
Assignee: ConocoPhillips Company
G01N33/287E21B49/005E21B49/088G01N33/2823
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Quick Facts
Patent No.
US 12,669,494
App. No.
18/060,838
Filed
Dec 1, 2022
Granted
Jun 30, 2026
Kind
B2
Art Unit
1758
USPC
436/123
Abstract

The disclosure describes a method to indirectly measure the amount of elemental sulfur or amorphous dithiazine in a reservoir sample by converting them to H 2 S gas. The H 2 S is captured via caustic cyanide solution and quantified by analytical methods and correspond to the concentration of elemental sulfur or amorphous dithiazine. The method has particular applicability to determine where best to drill and avoid locations of high sulfur.

Claims (13)

1 . A method of producing oil, said method comprising:

a) obtaining a plurality of samples, each sample from a known location in an oil reservoir and containing MEA or a triazine, or MEA or a triazine being added thereto;

b) optionally analyzing each of said plurality of samples or portion thereof to determine a first amount of H 2 S remaining unreacted with said MEA or triazine after step a);

c) analyzing each of said plurality of samples or portion thereof to determine an amount of dithiazine and correlating said amount of dithiazine to a second amount of H 2 S;

d) analyzing each of said plurality of samples or portion thereof for an amount of amorphous dithiazine (a-DTZ) by treatment with a reductive mercaptan solution to convert a-DZT to H 2 S and measuring a third amount of H 2 S and correlating said third amount of H 2 S to said amount of a-DTZ in said plurality of samples;

e) calculating a total amount of H 2 S in a each sample from a each said known location by adding said optional first amount of H 2 S from step b), said second amount of H 2 S from step c), and said third amount of H 2 S from step d), thereby determining one or more highest H 2 S content location(s) in said reservoir and one or more sweeter content location(s);

f) producing oil from said one or more sweeter content location(s) as determined in step e); and

g) wherein said produced oil has less H 2 S than a method of producing oil from said reservoir without steps a) through f).

2 . The method of claim 1 , wherein plurality of samples are drilling mud samples obtained while drilling an oil well or a test well.

3 . The method of claim 1 , wherein said plurality of samples are core samples.

4 . The method of claim 1 , wherein said reductive mercaptan solution comprises a mercaptan, an amine and an alcohol.

5 . The method of claim 1 , wherein said optional first, said second, and said third amounts of H 2 S are measured by a reaction with caustic cyanide and determining an amount of thiocyanate or isothiocyanate produced.

6 . The method of claim 5 , wherein said amount of thiocyanate or isothiocyanate is determined by reaction with iron or copper plus pyridine and measuring an amount of color produced.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 2, 2022
From: LOCKLEAR, JAY
To: CONOCOPHILLIPS COMPANY
Reel/Frame 061953/0909 →
Continuity (2)
Provisional Application 63287457 · Dec 8, 2021
Related Publication 20230176031A1 · Jun 8, 2023
References Cited (47)
US 3197396A · Stedman · 1965 [cited by applicant]
US 3708421A · Rippie · 1973 [cited by applicant]
US 4283270A · Mchale · 1981 [cited by applicant]
US 4478512A · Zoltner · 1984 [cited by applicant]
US 4978512A · Dillon · 1990 [cited by applicant]
US 5104557A · Lindstrom · 1992 [cited by applicant]
US 5160413A · Allison · 1992 [cited by applicant]
US 5199978A · Poirier et al. · 1993 [cited by applicant]
US 5585334A · Shaw · 1996 [cited by applicant]
US 5618408A · Poirier et al. · 1997 [cited by applicant]
US 6808919B2 · Ranson et al. · 2004 [cited by applicant]
US 6939717B2 · Jiang · 2005 [cited by examiner]
US 8920568B2 · Taylor · 2014 [cited by applicant]
US 8920586B2 · Poulakis · 2014 [cited by applicant]
US 9612204B2 · Locklear et al. · 2017 [cited by applicant]
US 10392271B2 · Janson et al. · 2019 [cited by applicant]
US 10564142B2 · Oduro · 2020 [cited by applicant]
US 10626334B2 · Bertrand · 2020 [cited by applicant]
US 11199078B2 · Sharma et al. · 2021 [cited by applicant]
US 20050238556A1 · Pakulski et al. · 2005 [cited by applicant]
US 20080308463A1 · Keckler · 2008 [cited by applicant]
US 20130149788A1 · Sacks et al. · 2013 [cited by applicant]
US 20140158876A1 · Jones · 2014 [cited by examiner]
US 20140171721A1 · Bertrand · 2014 [cited by applicant]
US 20150267113A1 · Ramachandran et al. · 2015 [cited by applicant]
US 20170269054A1 · Horton · 2017 [cited by examiner]
US 20210102932A1 · Locklear et al. · 2021 [cited by applicant]
US 20220112433A1 · Locklear et al. · 2022 [cited by applicant]
US 20220112443A1 · Locklear et al. · 2022 [cited by applicant]
WO 2008049188A1 · 2008 [cited by applicant]
WO 2018001604A1 · 2018 [cited by applicant]
Pineiro. Raman and DFT Study of the H2S Scavenger Reaction of HET-TRZ under Simulated Contactor Tower Conditions. 2021. (Year: 2021). [cited by examiner]
International Search Report for PCT/US22/80755 dated Apr. 25, 2023. (Attached). [cited by applicant]
Taylor, G. N.; Matherly, R. “Use of portable analytical methods to determine the stoichiometry of reaction for hexahydrotriazine-based hydrogen sulfide.” Anal Chem (2014) 86, 4879-4882. [cited by applicant]
Saleh, T. A. “Characterization, determination and elimination technologies for sulfur from petroleum: Toward cleaner fuel and a safe environment.” Trends in Environmental Anal. Chem. (2020) vol. 25, e0080. [cited by applicant]
Long, J. H. “A textbook of elementary analytical chemistry qualitative and volumetric.” (1910). [cited by applicant]
Taylor, G. N.; Matherly, R. Structural elucidation of solid byproduct from the useof 1,3,5-Tris(hydroxyalkyl) hexahydro-s-triazine based hydrogen sulfide scavengers. Industrial &Engineering Chemical Reserach. 2011, 50, … [cited by applicant]
Kwasniewski,, M.; Allison, R. B.; Wilcox, W. F.; Sacks, G. .L “Convenient, inexpensive quantification of elemental sulfur by simultaneous in situ reduction and calorimetric detection.” Anal. Chim. Acta. 2011, 703 (1), 5… [cited by applicant]
ASTM D2622-16 Standard test method for sulfur in petroleum products by wavelength dispersive X-ray Fluorescence Spectrometry, 2016. [cited by applicant]
ASTM D5623-19 “Standard test method for sulfur compounds in light petroleum liquids by gas chromatography and sulfur selective detection,” 2019. [cited by applicant]
ASTM D5453-19a “Standard test method for determination of total sulfur in light hydrocarbons, spark ignition engine uel diesel engine fuel, and engine oil by ultraviolet fluorescence,” 2019. [cited by applicant]
ASTM D4292-17 “Standard test method for determination of vibrated bulk density of calcined petroleum coke,” 2017. [cited by applicant]
ASTM D129-18 “Standard test method for sulfur in petroleum products (general high pressure decomposition device method),” 2018. [cited by applicant]
Supplementary Partial European Search Report for European Application No. EP 22905251 dated Nov. 7, 2025. [cited by applicant]
Agbroko, O. W., et al. “A comprehensive review of H2S scavenger technologies from Oil and gas stream.” ChemBioEng Rev, 4, No. 6, 339-359 (2017). [cited by applicant]
Chakraborty, S., et al. “Effective removal of hydrogen sulfide and mercaptans in oilfield applications.” Paper No. SPE-184589-MS, Paper presented at the SPE International Conference on Oilfield Chemistry, Montgomery, Te… [cited by applicant]
Wylde, J. J., et al. “Formation, chemical characterization, and oxidative dissolution of amorphous polymeric dithiazine (apDTZ) during the use of the H2S scavenger monoethanolamine-triazine.” Energy Fuels, 34, 9923-9931… [cited by applicant]