# US 10,308,860 B2 · Compositions and methods for filter cake removal > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,860 B2 - Document ID: US10308860B2 - Status: Granted - Kind: B2 - Application number: 15/175,812 - Filed: 2016-06-07 - Published: 2016-12-15 - Granted: 2019-06-04 - Earliest claimed: 2015-06-15 - Assignees: Ethical Solutions, LLC - Applicants: Ethical Solutions, LLC - Inventors: Daniel J. Socci; Jennifer L. Holcomb - Web page: https://patentgrep.com/patent/US10308860B2 ## CPC - C09K 8/52: Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning - C09K 8/03: Specific additives for general use in well-drilling compositions - C09K 8/58: Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids - C09K 8/706: {Encapsulated breakers} - C09K 8/92: characterised by their form or by the form of their components, e.g. encapsulated material (C09K8/70 takes precedence) - C09K 2208/26: Gel breakers other than bacteria or enzymes - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE ## Abstract Compositions for removing filter cake from a subterranean borehole and methods for degrading filter cake and filter cake removal are provided. The composition contains an encapsulated peroxygen (e.g., acrylic resin coated ammonium persulfate), a surfactant (e.g., nonionic surfactant), and optionally an unencapsulated peroxygen. The method (e.g., a one-step method) involves contacting the filter cake with the composition, and allowing the composition to remain in contact with the filter cake for a period of time sufficient to degrade the filter cake. The reaction of the composition with the filter cake results in acidic conditions, thereby eliminating any need for follow up acid treatments. The composition is stable enough to effectively remove filter cake at temperatures up to 250° F. or greater. Through filter cake removal, the method provides for increased flow, production, and/or recovery of oil and gas hydrocarbons from a subterranean formation. ## Claims ### Claim 1 A method of removing filter cake from a subterranean borehole, the method comprising: drilling a borehole with a drill-in fluid to form a filter cake; contacting the filter cake with a composition comprising (a) an encapsulated persulfate; and (b) a nonionic surfactant, wherein the encapsulated persulfate is present in an amount from about 0.01 to about 20 weight percent, and the nonionic surfactant is present in an amount from about 0.01 to about 50 weight percent, based on the total weight of the composition, when the composition is introduced into the borehole; and allowing the composition to remain downhole for a period of time sufficient to degrade the filter cake; wherein the contacting the filter cake with the composition generates acidic conditions, without addition of an acid; and wherein the persulfate chemically breaks down the filter cake via direct oxidation or free radical oxidation. ### Claim 2 (depends on 1) The method of claim 1, further comprising removing the degraded filter cake from the subterranean borehole. ### Claim 3 (depends on 1) The method of claim 1, wherein the composition further comprises a variable density brine. ### Claim 4 (depends on 1) The method of claim 1, wherein at least one component of the composition is mixed with fresh water, brine water, formation water with potassium chloride or other salts added, or combinations thereof, prior to introduction into the subterranean borehole. ### Claim 5 (depends on 1) The method of claim 1, wherein the encapsulated persulfate is selected from the group consisting of encapsulated sodium persulfate, encapsulated potassium persulfate, encapsulated ammonium persulfate, and combinations thereof. ### Claim 6 (depends on 1) The method of claim 1, wherein the encapsulated persulfate is cured acrylic resin encapsulated persulfate. ### Claim 7 (depends on 1) The method of claim 1, wherein the encapsulated persulfate is coated ammonium persulfate. ### Claim 8 (depends on 1) The method of claim 1, wherein the encapsulated persulfate provides a controlled time release of the persulfate. ### Claim 9 (depends on 1) The method of claim 1, wherein the persulfate from the encapsulated persulfate decomposes from a direct reduction reaction, a surface catalyzed reaction, and/or a free radical decomposition reaction. ### Claim 10 (depends on 1) The method of claim 1, wherein: the nonionic surfactant is selected from the group consisting of an ethoxylated plant oil based surfactant, a fatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid amide ethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, an alkyl polyglucoside, a polyalcohol ethoxylate, a sorbitan ester, a soy alkyltrimethyl ammonium chloride, an ethoxylated coco fatty acid, an ethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylated castor oil, and combinations thereof; or the nonionic surfactant is selected from the group consisting of a fatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, an alkyl polyglucoside, a polyalcohol ethoxylate, a soy alkyltrimethyl ammonium chloride, a monococoate, and combinations thereof; or the nonionic surfactant is selected from the group consisting of an ethoxylated coco fatty acid, an ethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylated castor oil, a monococoate, and combinations thereof; or the nonionic surfactant comprises a sorbitan ester selected from the group consisting of sorbitan monooleate having a Hydrophile-Lipophile Balance (HLB) range from about 2.8 to about 8.8; sorbitan monolaurate having a Hydrophile-Lipophile Balance (HLB) range from about 4.6 to about 12.6; sorbitan monopalmitate having a Hydrophile-Lipophile Balance (HLB) range from about 2.5 to about 10.5; and sorbitan monostearate having a Hydrophile-Lipophile Balance (HLB) range from about 2.7 to about 8.7; or the nonionic surfactant comprises an ethoxylated sorbitan ester selected from the group consisting of a polyethylene glycol (PEG) sorbitan monooleate having a range of about 2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; a polyethylene glycol (PEG) sorbitan monolaurate having a range of about 2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; a polyethylene glycol (PEG) sorbitan monopalmitate having a range of about 2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; and a polyethylene glycol (PEG) sorbitan monostearate having a range of about 2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20. ### Claim 11 (depends on 10) The method of claim 10, wherein the ethoxylated coco fatty acid is a polyethylene glycol (PEG) coco fatty acid having a range of about 5 to about 40 PEG groups, and a Hydrophile-Lipophile Balance (HLB) range from about 10 to about 19; the ethoxylated castor oil is a polyethylene glycol (PEG) castor oil having a range of about 2.5 to about 40 PEG groups, and a Hydrophile-Lipophile Balance (HLB) range from about 2.1 to about 16; the ethoxylated cocoamide is a polyethylene glycol (PEG) cocamide having a range of about 2 to about 20 PEG groups, and a Hydrophile-Lipophile Balance (HLB) range from about 2 to about 19. ### Claim 12 (depends on 1) The method of claim 1, further comprising a chelate, wherein the chelate is selected from the group consisting of a mono-, di-, tri- or tetra-sodium ethylenediaminetetraacetic acid (EDTA), a mono-, di-, tri- or tetra-potassium ethylenediaminetetraacetic acid (EDTA), sodium ethylenediamine-N,N′-disuccinic acid (EDDS), and combinations thereof. ### Claim 13 (depends on 1) The method of claim 1, further comprising a cosolvent, wherein the cosolvent is selected from the group consisting of a terpene, methyl soyate, ethyl lactate, methyl lactate, ethyl acetate, and combinations thereof. ### Claim 14 (depends on 1) The method of claim 1, wherein the encapsulated persulfate and the nonionic surfactant are added simultaneously or sequentially to the composition. ### Claim 15 (depends on 1) The method of claim 1, wherein the composition is applied to the subterranean borehole as, or in combination with, a drilling fluid, treatment fluid, stimulation fluid, fracturing fluid, a fluid used in an enhanced oil recovery technique, or a combination thereof. ### Claim 16 (depends on 1) The method of claim 1, further comprising: allowing the composition to contact blockage or damage in the subterranean borehole, so that the damage or blockage is altered, removed, degraded, and/or dissolved, so that a permeability, a relative permeability, and/or an absolute permeability of the subterranean formation is increased, causing an increase in the production rates and/or recovery of hydrocarbons. ### Claim 17 A method of removing filter cake from a subterranean borehole, said method comprising: drilling a borehole with a drill-in fluid to form a filter cake; contacting the filter cake with a composition comprising (a) an encapsulated persulfate; and (b) a nonionic surfactant; and (c) an unencapsulated persulfate, wherein the encapsulated persulfate is present in an amount from about 0.01 to about 20 weight percent, the nonionic surfactant is present in an amount from about 0.01 to about 50 weight percent, and the unencapsulated persulfate is present in an amount from about 0.01 to about 20 weight percent, based on the total weight of the composition, when the composition is introduced into the borehole; and allowing the composition to remain downhole for a period of time sufficient to degrade the filter cake; wherein the contacting the filter cake with the composition generates acidic conditions, without addition of an acid; and wherein the persulfate chemically breaks down the filter cake via direct oxidation or free radical oxidation.