WO2025240501A1

WO2025240501A1 - Mitigation of hydrogen sulfide scavenging reaction solids fouling

Info

Publication number: WO2025240501A1
Application number: PCT/US2025/029175
Authority: WO
Inventors: Hitesh Bagaria; Moshood ADEWALE
Original assignee: BL Technologies Inc
Current assignee: BL Technologies Inc
Priority date: 2024-05-13
Filing date: 2025-05-13
Publication date: 2025-11-20
Anticipated expiration: 2026-11-13

Abstract

A method of removing hydrogen sulfide from an industrial process fluid, the method comprising adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of a formaldehyde-based sulfide scavenger and a bisulfite and/or a phosphonium.

Description

MITIGATION OF HYDROGEN SULFIDE SCAVENGING REACTION SOLIDS FOULING

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the priority benefit of U.S. Provisional Patent Application Serial No. 63/646,123 filed May 13, 2024, the entirety of which is incorporated herein by reference.

FIELD

[0002] The disclosed technology relates to scavenging and/or removal of hydrogen sulfide from industrial process fluids. In particular, the disclosed technology relates to scavenging and/or removal of hydrogen sulfide from industrial process fluids using treatment compositions including formaldehyde-based sulfide scavengers and bisulfites and/or phosphoniums.

BACKGROUND

[0003] Formaldehyde-based hydrogen sulfide scavengers are a cost-effective chemical solution for removing hydrogen sulfide from oil and gas production streams due to their high scavenging capacity and low cost. However, one of the undesirable outcomes of using formaldehyde-based hydrogen sulfide scavengers is the formation of hydrogen sulfide- scavenger reaction product solids that may foul downstream units. Hence, there is a need for scavenger compositions that inhibit and/or mitigate the fouling caused by hydrogen sulfide scavenger reaction product solids.

SUMMARY

[0004] The disclosed technology provides for compositions and methods for removing hydrogen sulfide from an industrial process fluid while preventing the formation or deposition of hydrogen sulfide reaction solids.

[0005] Various aspects of the disclosure relate to a method of removing hydrogen sulfide from an industrial process fluid, the method comprising adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of (i) a formaldehyde-based sulfide scavenger; and (ii) a bisulfite, or a phosphonium, or mixtures thereof. [0006] Various aspects of the disclosure additionally relate to a method of preventing formation of hydrogen sulfide reaction solids in an industrial process fluid, the method comprising adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of (i) a formaldehyde-based sulfide scavenger; and (ii) a bisulfite, or a phosphonium, or mixtures thereof.

[0007] Various aspects of the disclosure further relate to a treatment composition for preventing formation of hydrogen sulfide reaction solids in an industrial process fluid, wherein the treatment composition comprises a mixture of (i) a formaldehyde-based sulfide scavenger; and (ii) a bisulfite, or a phosphonium, or mixtures thereof.

BRIEF DESCRIPTION OF THE FIGURES

[0008] Those of skill in the art will understand that the figures, described below, are for illustrative purposes only. The figures are not intended to limit the scope of the present teachings in any way.

[0009] FIG. 1 illustrates the hydrogen sulfide scavenging performance of treatment compositions in accordance with embodiments of the present disclosure.

[0010] FIG. 2 illustrates the solids content of a sample process fluid after addition of treatment compositions in accordance with embodiments of the present disclosure.

[0011] FIG. 3 illustrates the precipitation of sulfide scavenger reaction solids in a sample process fluid treated only with a formaldehyde -based sulfide scavenger.

[0012] FIG. 4 illustrates the reduced precipitation of sulfide scavenger reaction solids in a sample process fluid treated with a treatment composition in accordance with an embodiment of the present disclosure.

DETAILED DESCRIPTION

[0013] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges stated herein unless context or language indicates otherwise. Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions and the like, used in the specification and the claims, are to be understood as modified in all instances by the term “about”.

[0014] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

[0015] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article or apparatus that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0016] The singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0017] The disclosed technology provides for compositions and methods for removing hydrogen sulfide from an industrial process fluid while preventing the formation of hydrogen sulfide reaction solids.

[0018] The compositions and methods disclosed herein have been found to be effective in reducing the formation of hydrogen sulfide reaction product solids, while maintaining scavenging capacity. More specifically, it was found that treatment compositions comprising formaldehyde-based sulfide scavengers and low levels of bisulfite and/or phosphonium reduced the precipitation of high sulfur reaction products. Without being bound by theory, bisulfite and/or phosphonium, which are known to react with free formaldehyde, may stabilize these products by forming an adduct.

[0019] As used herein, the term “industrial process fluid” refers to any liquid or gas used within an industrial process to carry out a specific function or achieve a desired outcome. These fluids can range from water and various chemicals to gases like nitrogen or compressed air, depending on the requirements of the process.

[0020] In various aspects of the disclosed technology, methods of removing hydrogen sulfide from an industrial process fluid are disclosed. In various aspects, the methods may comprise adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of a formaldehyde -based sulfide scavenger, and a bisulfite and/or a phosphonium. [0021] In various aspects, suitable formaldehyde -based sulfide scavengers may include any formaldehyde-based compound that is effective in scavenging sulfide ions. In some aspects, suitable formaldehyde-based sulfide scavengers may include formaldehyde-based polymers, formaldehyde-based resins, or mixtures thereof. In other aspects, suitable formaldehyde-based sulfide scavengers may include hexahydrotriazines; oxazolidines; an alcohol condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol-HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or their combinations; an amide-HCHO condensate with urea, the amide, and optionally other amines; secondary amine-adducts; polyol/amide-HCHO condensates such as EDDM; glycerolformaldehyde reaction products; urea-HCHO condensate; and the like; and combinations thereof.

[0022] In various aspects, suitable bisulfites may include alkali metal bisulfites, such as sodium bisulfite; alkaline earth metal bisulfites; ammonium bisulfites, or mixtures thereof.

[0023] In various aspects, suitable phosphoniums may include tetrakis hydroxymethyl phosphonium sulfates or chloride.

[0024] In various aspects, the bisulfite and/or phosphonium is present at a low level in the treatment composition, such as in an amount of less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 10%, or less than 5%, or less than 1% by weight of the treatment composition. In some aspects, the treatment composition comprises bisulfite and/or phosphonium in amount of about 0.5% to about 50% by weight of the treatment composition, or an amount of about 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by weight of the treatment composition, or 5% to about 25% by weight of the treatment composition or about 10% to about 20% by weight of the treatment composition, or any percentage in between any of these values.

[0025] In various aspects, examples of industrial process fluids that may be treated with the treatment compositions of the disclosed technology may include single or multiphase oil, water or gas production fluids, including deep water multiphase production fluids; single or multiphase refinery fluids; industrial wastewater fluids; industrial process streams; and the like.

[0026] In various aspects of the disclosed technology, methods of preventing formation of hydrogen sulfide reaction solids in an industrial process fluid are disclosed. In various aspects, the methods may comprise adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of a formaldehyde-based sulfide scavenger, and a bisulfite and/or phosphonium. In other aspects, the methods may comprise optionally adding an antimicrobial additive, such as a biocide; corrosion inhibitors; scale inhibitors; dispersants; and the like, or mixtures thereof, to the industrial process fluid.

[0027] In various aspects, suitable formaldehyde -based sulfide scavengers may include any formaldehyde-based compound that is effective in scavenging sulfide ions. In some aspects, suitable formaldehyde-based sulfide scavengers may include formaldehyde-based polymers, formaldehyde-based resins, or mixtures thereof. In other aspects, suitable formaldehyde-based sulfide scavengers may include hexahydrotriazines; oxazolidines; a condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol-HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or their combinations; an amide-HCHO condensate with urea, the amide, and optionally other amines; secondary amine- HCHO adducts; polyol/amide-HCHO condensates such as EDDM; glycerol-formaldehyde reaction products; urea-HCHO condensate; and the like; and combinations thereof.

[0028] In various aspects, suitable bisulfites may include alkali metal bisulfites, such as sodium bisulfite; alkaline earth metal bisulfites; ammonium bisulfites, or mixtures thereof.

[0029] In various aspects, suitable phosphoniums may include tetrakis hydroxymethyl phosphonium sulfates or chloride.

[0030] In various aspects, the bisulfite and/or phosphonium is present at a low level in the treatment composition, such as in an amount of less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 10%, or less than 5%, or less than 1% by weight of the treatment composition. In some aspects, the treatment composition comprises bisulfite and/or phosphonium in amount of about 0.5% to about 50% by weight of the treatment composition, or an amount of about 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by weight of the treatment composition, or 5% to about 25% by weight of the treatment composition or about 10% to about 20% by weight of the treatment composition, or any percentage in between any of these values.

[0031] In various aspects of the disclosed technology, treatment compositions for preventing formation of hydrogen sulfide reaction solids in an industrial process fluid are disclosed. In various aspects, the treatment composition may comprise a mixture of a formaldehyde-based sulfide scavenger, and a bisulfite and/or a phosphonium.

[0032] In various aspects, suitable formaldehyde -based sulfide scavengers may include any formaldehyde-based compound that is effective in scavenging sulfide ions. In some aspects, suitable formaldehyde-based sulfide scavengers may include formaldehyde-based polymers, formaldehyde-based resins, or mixtures thereof. In other aspects, suitable formaldehyde-based sulfide scavengers may include hexahydrotriazines; oxazolidines; a condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol-HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or their combinations; an amide-HCHO condensate with urea, the amide, and optionally other amines; secondary amine- HCHO adducts; polyol/amide-HCHO condensates such as EDDM; glycerol-formaldehyde reaction products; urea-HCHO condensate; and the like; and combinations thereof.

[0033] In various aspects, suitable bisulfites may include alkali metal bisulfites, such as sodium bisulfite; alkaline earth metal bisulfites; ammonium bisulfites, or mixtures thereof.

[0034] In various aspects, suitable phosphoniums may include tetrakis hydroxymethyl phosphonium sulfates or chloride.

[0035] In various aspects, the bisulfite and/or phosphonium is present at a low level in the treatment composition, such as in an amount of less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 10%, or less than 5%, or less than 1% by weight of the treatment composition. In some aspects, the treatment composition comprises bisulfite and/or phosphonium in amount of about 0.5% to about 50% by weight of the treatment composition, or an amount of about 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by weight of the treatment composition, or 5% to about 25% by weight of the treatment composition or about 10% to about 20% by weight of the treatment composition, or any percentage in between any of these values.

[0036] In various aspects, the treatment composition may further include an antimicrobial additive, such as a biocide; corrosion inhibitors; scale inhibitors; dispersants; and the like, or mixtures thereof.

EXAMPLES

[0037] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology or limit the scope to any particular embodiments.

[0038] Formulations

[0039] The following formulations were tested for hydrogen sulfide (H2S) scavenging performance and H2S scavenger reaction solids formation: [0040] Example 1

[0041] H2S Scavenging Performance

[0042] Hydrogen sulfide was continuously bubbled into a solution containing CO2 to form a saturated solution of H2S and CO2. The scavenger compositions of Formulas 1-3 were injected and scavenging performance monitored at a temperature of 70°C and 70% water cut. As shown in FIG. 1, the performance of the scavenger compositions of Formulas 1 and 2 were minimally impacted by the inclusion of sodium bisulfite and ammonium bisulfite, respectively, as confirmed by duplicate runs (runs -1 and -2).

[0043] Example 2

[0044] H2S Scavenger Reaction Solids by Filtration

[0045] Hydrogen sulfide was continuously bubbled into a solution containing CO2 to form a saturated solution of H2S and CO2. The scavenger compositions of Formulas 1-3 were injected and solids content was monitored by filtration. As shown in FIG. 2, solids content decreased in the following order: Formula 1 > Formula 3 > Formula 2, as confirmed by duplicate runs (runs -1 and -2).

[0046] Example 3

[0047] The scavenger compositions of Formulas 1 and 3 were added to sample process fluid aliquots containing 70% water and 30% oil. As shown in FIG. 3, substantial precipitation of H2S scavenger reaction solids was observed after addition of the scavenger composition of Formula 1. However, as shown in FIG. 4, minimal precipitation of H2S scavenger reaction solids was observed after addition of the scavenger composition of Formula 3.

[0048] While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

Claims

1. A method of removing hydrogen sulfide from an industrial process fluid, the method comprising adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of

(i) a formaldehyde-based sulfide scavenger; and

(ii) a bisulfite, or a phosphonium, or mixtures thereof.

2. The method of claim 1, wherein the formaldehyde-based sulfide scavenger is selected from a formaldehyde-based polymer, a formaldehyde -based resin, and mixtures thereof.

3. The method of claim 1, wherein the formaldehyde-based sulfide scavenger is selected from a hexahydro triazine; an oxazolidine; a condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol-HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or their combinations; an amide-HCHO condensate with urea; secondary amine-HCHO adducts; and combinations thereof.

4. The method of any one of claims 1-3, wherein the treatment composition comprises a bisulfite, and wherein the bisulfite is selected from an alkali metal bisulfite, an alkaline earth metal bisulfite, an ammonium bisulfite, or mixtures thereof.

5. The method of claim 4, wherein the bisulfite is an ammonium bisulfite.

6. The method of any one of claims 1-3, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is selected from alkyl, hydroxyalkyl or alkylhydroxyalkyl phosphonium quaternary salt.

7. The method of claim 6, wherein the phosphonium is tetrakis hydroxymethyl phosphonium sulfate (THPS).

8. The method of any one of claims 1-5, wherein the treatment composition comprises bisulfite, and wherein the bisulfite is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

9. The method of claim 8, wherein the bisulfite is present in an amount of about 5% by weight of the treatment composition.

10. The method of claim 1, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

11. The method of claim 10, wherein the phosphonium is present in an amount of about 20% by weight of the treatment composition.

12. The method of any one of claims 1-11, wherein the industrial process fluid comprises a single or multiphase oil, water and gas production fluid; a single or multiphase refinery fluid; or an industrial wastewater fluid.

13. A method of preventing formation of hydrogen sulfide reaction solids in an industrial process fluid, the method comprising adding a treatment composition to the industrial process fluid, wherein the treatment composition comprises a mixture of

(i) a formaldehyde-based sulfide scavenger; and

(ii) a bisulfite, or a phosphonium, or mixtures thereof.

14. The method of claim 13, wherein the formaldehyde-based sulfide scavenger is selected from a formaldehyde-based polymer, a formaldehyde -based resin, and mixtures thereof.

15. The method of claim 13, wherein the formaldehyde-based sulfide scavenger is selected from a hexahydro triazine; an oxazolidine; a condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol-HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or combinations thereof; an amide-HCHO condensate with urea; secondary amine-HCHO adducts; and combinations thereof.

16. The method of any one of claims 13-15, wherein the treatment composition comprises bisulfite, and wherein the bisulfite is selected from an alkali metal bisulfite, an alkaline earth metal bisulfite, an ammonium bisulfite, or mixtures thereof.

17. The method of claim 16, wherein the bisulfite is an ammonium bisulfite.

18. The method of any one of claims 13-15, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is selected from alkyl, hydroxyalkyl or alkylhydroxyalkyl phosphonium quaternary salt.

19. The method of claim 18, wherein the phosphonium is tetrakis hydroxymethyl phosphonium sulfate (THPS).

20. The method of any one of claims 13-17, wherein the treatment composition comprises a bisulfite, and wherein the bisulfite is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

21. The method of claim 20, wherein the bisulfite is present in an amount of about 5% by weight of the treatment composition.

22. The method of claim 13, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

23. The method of claim 21, wherein the phosphonium is present in an amount of about 20% by weight of the treatment composition.

24. The method of any one of claims 13-23, wherein the industrial process fluid comprises a single or multiphase oil, water or gas production fluid; a single or multiphase refinery fluid; or an industrial wastewater fluid.

25. The method of any one of claims 13-24, wherein the method further comprises adding an antimicrobial additive, a corrosion inhibitor, a scale inhibitor, a dispersant, or mixtures thereof.

26. The method of claim 25, wherein the antimicrobial additive comprises a biocide.

27. A treatment composition for preventing formation of hydrogen sulfide reaction solids in an industrial process fluid, wherein the treatment composition comprises a mixture of

(i) a formaldehyde-based sulfide scavenger; and

(ii) a bisulfite, or a phosphonium, or mixtures thereof.

28. The treatment composition of claim 27, wherein the formaldehyde-based sulfide scavenger is selected from a formaldehyde -based polymer, a formaldehyde-based resin, and mixtures thereof.

29. The treatment composition of claim 27, wherein the formaldehyde-based sulfide scavenger is a hexahydro triazine; an oxazolidine; a condensate prepared by the reaction of HCHO with alkanol amine or alkyl amine or ether amines or their combinations; an alcohol- HCHO condensate prepared by reaction of HCHO with methanol, ethanol, ethylene glycol, glycerol, propylene glycol or their combinations; an amide-HCHO condensate with urea; the amide and optionally other amines; secondary amine-HCHO adducts; and combinations thereof.

30. The treatment composition of any one of claims 27-29, wherein the treatment composition comprises bisulfite, and wherein the bisulfite is selected from an alkali metal bisulfite, an alkaline earth metal bisulfite, an ammonium bisulfite, or mixtures thereof.

31. The treatment composition of claim 30, wherein the bisulfite is an ammonium bisulfite.

32. The treatment composition of any one of claims 27-29, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is selected from alkyl, hydroxyalkyl or alkyl-hydroxyalkyl phosphonium quaternary salt.

33. The treatment composition of claim 32, wherein the phosphonium is tetrakis hydroxymethyl phosphonium sulfate (THPS).

34. The treatment composition of any one of claims 27-31, wherein the treatment composition comprises bisulfite, and wherein the bisulfite is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

35. The treatment composition of claim 34, wherein the bisulfite is present in an amount of about 5% by weight of the treatment composition.

36. The treatment composition of claim 27, wherein the treatment composition comprises phosphonium, and wherein the phosphonium is present in an amount of about 0.5% to about 50% by weight of the treatment composition.

37. The treatment composition of claim 36, wherein the phosphonium is present in an amount of about 20% by weight of the treatment composition.

38. The treatment composition of any one of claims 27-37, wherein the treatment composition further comprises an antimicrobial additive, a corrosion inhibitor, a scale inhibitor, a dispersant, or mixtures thereof.

39. The treatment composition of claim 38, wherein the antimicrobial additive comprises a biocide.