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US-12618014-B2 - Compounds for breaking emulsions

US12618014B2US 12618014 B2US12618014 B2US 12618014B2US-12618014-B2

Abstract

A demulsifying agent may comprise the structure R 1 may be a hydrocarbyl group or heterohydrocarbyl group comprising from 1 to 20 carbon atoms. m may be from 2 to 10, n may be from 5 to 20, and p may be from 2 to 15. R 2 may comprise a residue of propylene oxide. R 3 may comprise a residue of glycidol. Embodiments of the present disclosure may further comprise methods of making the demulsifying agent and methods of using the demulsifying agent to demulsify a hydrocarbon emulsion.

Inventors

  • Manal Al-Eid
  • Laila S. Alsaihati
  • Donya A. Alsewdan
  • Rashed Mohammad Aleisa
  • Muhammad Imran Ulhaq
  • Shaikh Asrof Ali

Assignees

  • SAUDI ARABIAN OIL COMPANY
  • KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS

Dates

Publication Date
20260505
Application Date
20230503

Claims (20)

  1. 1 . A demulsifying agent comprising the structure wherein: R 1 is a hydrocarbyl group or heterohydrocarbyl group comprising from 1 to 20 carbon atoms; subscript “m” is from 2 to 10, subscript “n” is from 5 to 20; subscript “p” is from 2 to 15; R 2 comprises a residue of propylene oxide; and R 3 comprises a residue of glycidol.
  2. 2 . The demulsifying agent of claim 1 , wherein R 2 is a hydrocarbyl group of structure —(—CH 2 —CHCH 3 —O—).
  3. 3 . The demulsifying agent of claim 1 , wherein each R 3 group is independently a hydrocarbyl group of structure IV, V, or VI; wherein
  4. 4 . The demulsifying agent of claim 1 , wherein R 1 is a hydrocarbyl group with from 5 to 15 carbon atoms.
  5. 5 . The demulsifying agent of claim 1 , wherein a ratio of subscripts m:p is from 1:2 to 1:15.
  6. 6 . The demulsifying agent of claim 1 , wherein a ratio of subscripts m:n is from 1:5 to 1:20.
  7. 7 . The demulsifying agent of claim 1 , wherein a ratio of subscripts n:p is from 10:1 to 1:3.
  8. 8 . The demulsifying agent of claim 1 , wherein a weight averaged molecular weight of the demulsifying agent is from 1,000 g/mol to 10,000 g/mol.
  9. 9 . The demulsifying agent of claim 1 , wherein: R 2 is a hydrocarbyl group of structure —(—CH 2 —CHCH 3 —O—); R 1 is a hydrocarbyl group with from 5 to 15 carbon atoms; a ratio of subscripts n:p is from 5:1 to 5:3; a ratio of subscripts m:n is from 1:8 to 1:12; a ratio of subscripts m:p is from 1:3 to 1:5; a weight averaged molecular weight of the demulsifying agent is from 1,000 g/mol to 10,000 g/mol; and wherein each R 3 group is independently a hydrocarbyl group of structure IV, structure V, or structure VI; where
  10. 10 . A method of making a demulsifying agent, the method comprising: combining novolak solids with an aprotic solvent, a weak base, and an alcohol to form a novolak solution; drying the novolak solution to form a novolak residue; combining the novolak residue with propylene oxide under stirring to form a novolak-propylene oxide solution; reacting the novolak-propylene oxide solution to form a novolak-PPO solution; combining the novolak-PPO solution with glycidol to form a novolak-PPO-glycidol solution; reacting the novolak-PPO-glycidol solution to form a novolak-PPO-HPG solution; drying the novolak-PPO-HPG solution to form the demulsifying agent, wherein the demulsifying agent comprises the structure wherein: R 1 is a hydrocarbyl group or heterohydrocarbyl group comprising from 1 to 20 carbon atoms; subscript “m” is from 2 to 10, subscript “n” is from 5 to 20; subscript “p” is from 2 to 15; R 2 comprises a residue of propylene oxide; and R 3 comprises a residue of glycidol.
  11. 11 . A method of making the demulsifying agent of claim 10 , further comprising: combining a phenol compound with a first acid to form a phenol-acid solution; heating the phenol-acid solution at a temperature of about 80° C. for about 30 minutes; and combining paraformaldehyde with the phenol-acid solution to form a formaldehyde solution comprising the novolak solids.
  12. 12 . A method of making the demulsifying agent of claim 11 , where the phenol compound comprises p-nonylphenol.
  13. 13 . A method of making the demulsifying agent of claim 10 , wherein the aprotic solvent comprises dioxane.
  14. 14 . A method of making the demulsifying agent of claim 10 , where the weak base comprises potassium formate.
  15. 15 . A method of demulsifying a hydrocarbon emulsion, the method comprising combining a hydrocarbon feed with a demulsifying agent to form a hydrocarbon-demulsifying agent solution; wherein the hydrocarbon feed comprises water and hydrocarbons, wherein the demulsifying agent comprises the structure wherein: R 1 is a hydrocarbyl group or heterohydrocarbyl group comprising from 1 to 20 carbon atoms; subscript “m” is from 2 to 10, subscript “n” is from 5 to 20; subscript “p” is from 2 to 15; R 2 comprises a residue of propylene oxide; and R 3 comprises a residue of glycidol.
  16. 16 . The method of demulsifying a hydrocarbon emulsion of claim 15 , wherein the hydrocarbon feed comprises a crude oil.
  17. 17 . The method of demulsifying a hydrocarbon emulsion of claim 15 , wherein the hydrocarbon-demulsifying agent solution comprises from 10 to 200 ppm of the demulsifying agent.
  18. 18 . The method of demulsifying a hydrocarbon emulsion of claim 15 , wherein the hydrocarbon-demulsifying agent solution further comprises an aromatic compound, an alcohol, or both.
  19. 19 . The method of demulsifying a hydrocarbon emulsion of claim 18 , wherein the aromatic compound comprises xylene and the alcohol comprises methanol.
  20. 20 . The method of demulsifying a hydrocarbon emulsion of claim 15 , wherein the hydrocarbon feed is a water in oil emulsion.

Description

FIELD The present disclosure relates to compounds and processes for breaking an emulsion, and to processes for making said compounds. In particular, the present disclosure relates to demulsifying agents, methods of making demulsifying agents, and processes for using demulsifying agents for breaking hydrocarbon-water emulsions. TECHNICAL BACKGROUND The formation of emulsions is a common issue which can occur at many stages during the production and processing of crude oils. The presence of water in crude oil, such as in an emulsion can contribute to corrosion of refinery equipment, poisoning catalysts used in downstream processing facilities, and increasing pumping costs for the transportation of oil in pipelines. Additionally, the presence of water in the crude oil can cause excessive pressure drop in flow lines, tripping equipment in the gas oil separation plant (GOSP) offline. Accordingly, it is important to remove water from the crude oil at certain points in the crude oil production and upgrading process. Ethylene oxide grafted phenolic resins have long been used to break emulsions and remove water from crude oil. However, these emulsion breakers have insufficient performance. Additionally, ethylene oxide is a reactive, flammable gas which requires special process handling equipment. Additionally, ethylene oxide based demulsifying agents are insufficiently effective at breaking crude oil emulsions. Accordingly, more effective demulsifying agents which can be produced with reduced need for flammable, reactive gasses and special handling equipment are desired. BRIEF SUMMARY Embodiments of the present disclosure meet this need by providing environmentally friendly, hyper-branched copolymers of phenol-formaldehyde resins for use as demulsifying agents. Specifically, the demulsifying agents of the present disclosure may comprise phenol residues, residues of propylene oxide, and residues of glycidol. Without being limited by theory, it is believed that the demulsifying agents of the present disclosure perform better than prior demulsifying agents due to increased numbers of hydrophilic groups, since combining functional hyper-branched compounds with the phenol resin structure allows multiple hydrophilic groups to coexist in a single branch of the demulsifying agent. These hydrophilic groups are believed to bind to water molecules, facilitating the separation of oil in water emulsions. Additionally, these demulsifying agents do not require the use of flammable ethylene oxide. According to at least one aspect of the present disclosure, a demulsifying agent may comprise the structure R1 may be a hydrocarbyl group or heterohydrocarbyl group comprising from 1 to 20 carbon atoms. Subscript “m” may be from 2 to 10, subscript “n” may be from 5 to 20, and subscript “p” may be from 2 to 15. R2 may comprise a residue of propylene oxide R3 may comprise a residue of glycidol. According to at least one aspect of the present disclosure, a method of making a demulsifying agent may comprise combining novolak solids with an aprotic solvent, a weak base, and an alcohol to form a novolak solution; drying the novolak solution to form a novolak residue; combining the novolak residue with propylene oxide under stirring to form a novolak-propylene oxide solution; reacting the novolak-propylene oxide solution to form a novolak-PPO solution; combining the novolak-PPO solution with glycidol to form a novolak-PPO-glycidol solution; reacting the novolak-PPO-glycidol solution to form a novolak-PPO-HPG solution; and drying the novolak-PPO-HPG solution to form the demulsifying agent. According to at least one aspect of the present disclosure, a method of demulsifying a hydrocarbon emulsion may comprise combining a hydrocarbon feed with a demulsifying agent to form a hydrocarbon-demulsifying agent solution. The hydrocarbon feed may comprise water and hydrocarbons. Additional features and advantages of the aspects of the present disclosure will be set forth in the detailed description that follows and, in part, will be readily apparent to a person of ordinary skill in the art from the detailed description or recognized by practicing the aspects of the present disclosure. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which: FIG. 1 is a graphical depiction of electrospray ionization-mass spectrometry (ESI-MS) of some embodiments of the present disclosure. DETAILED DESCRIPTION The present disclosure is directed to demulsifying agents, methods of making demulsifying agents, and processes for demulsifying hydrocarbon feeds, such as crude oils. A demulsifying agent of the present disclosure may comprise a compound of structure I. R1 may be a hydrocarbyl group or heterohydrocarbyl group, R2 may comprise a residue