WO2023214360A1 - Pré-mélanges d'acides modifiés stabilisés - Google Patents

Pré-mélanges d'acides modifiés stabilisés Download PDF

Info

Publication number
WO2023214360A1
WO2023214360A1 PCT/IB2023/054673 IB2023054673W WO2023214360A1 WO 2023214360 A1 WO2023214360 A1 WO 2023214360A1 IB 2023054673 W IB2023054673 W IB 2023054673W WO 2023214360 A1 WO2023214360 A1 WO 2023214360A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
alkanolamine
composition
reconstituted
molar ratio
Prior art date
Application number
PCT/IB2023/054673
Other languages
English (en)
Inventor
Markus Weissenberger
Aryan Ghezelbashan
Nikita Chkolny
Original Assignee
Dorf Ketal Chemicals Fze
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dorf Ketal Chemicals Fze filed Critical Dorf Ketal Chemicals Fze
Publication of WO2023214360A1 publication Critical patent/WO2023214360A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen

Definitions

  • This invention relates to a method of stabilizing an aqueous composition of alkanolamine more specifically, where said composition is used for the on-site blending of a modified acid.
  • Acidizing is a type of stimulation treatment which is performed above or below the reservoir fracture pressure in an effort to initiate, restore or increase the natural permeability of the reservoir. Acidizing is achieved by pumping acid, predominantly hydrochloric acid, into the well to dissolve typically limestone, dolomite and calcite cement between the acid insoluble sediment grains of the reservoir rocks or to treat scale accumulation.
  • a matrix acid treatment is performed when acid is pumped into the well and into the pores of the reservoir formation below the fracture pressure.
  • the acids dissolve the sediments formation and/or mud solids that are inhibiting the permeability of the rock, enlarging the natural pores of the reservoir (wormholing) and stimulating the flow of hydrocarbons to the wellbore for recovery.
  • This type of acid treatment forms channels or fractures through which the hydrocarbons can flow, in addition to forming a series of wormholes.
  • a proppant is introduced into the fluid which assists in propping open the fractures, further enhancing the flow of hydrocarbons into the wellbore.
  • mineral and organic acids used to perform an acid treatment on wells.
  • the most common type of acid employed on wells to stimulate production is hydrochloric acid (HC1), which is useful in stimulating carbonate reservoirs.
  • hydrochloric acid produces hydrogen chloride gas which is toxic (potentially fatal) and corrosive to skin, eyes and metals. At levels above 50 ppm (parts per million) it can be Immediately Dangerous to Life and Health (IDHL). At levels from 1300-2000 ppm death can occur in 2-3 minutes.
  • acids When mixed with bases or higher pH fluids, acids will create a large amount of thermal energy (exothermic reaction) causing potential safety concerns and equipment damage, acids typically need to be blended with fresh water (due to their intolerance of highly saline water, causing potential precipitation of minerals) to the desired concentration requiring companies to pre -blend off-site as opposed to blending onsite with sea or produced water thereby increasing costs associated with transportation.
  • Conventional mineral acids used in a pH control situation can cause rapid degradation of certain polymers/additives requiring increased loadings or chemicals to be added to counter these negative effects.
  • Acids are used in the performance of many operations in the oil & gas industry and are considered necessary to achieve the desired production of various petroleum wells and associated equipment, maintain their respective systems and aid in certain drilling operational functions (i.e. freeing stuck pipe, filter cake treatments).
  • the associated dangers that come with using mineral acids are expansive and tasking to mitigate through controls whether they are chemically or mechanically engineered. Eliminating or even simply reducing the negative effects of strong acids while maintaining their usefulness is a struggle and risk for the industry.
  • companies are looking for alternatives that perform the required function without all or most of the drawbacks associated with the use of conventional acids.
  • compositions used in these various operations need to withstand high temperatures without losing their overall effectiveness.
  • These compositions must also be capable of being applied in operations over a wide range of temperatures while not or at least minimally affecting or corroding the equipment with which it comes in contact in comparison to a conventional mineral acid of which the corrosion effect at ultra-high temperatures is very difficult and expensive to control.
  • Offshore oil and gas operations are highly regulated due to the environmental concerns which arise from their operations and the potential for spills along with confined work spaces offering little chance of egress in the case of an incident.
  • the MEA aqueous composition would preferably be in a solution of pure MEA.
  • substantially pure MEA is fuming when in contact with air humidity and can thus be very dangerous to those handling it.
  • compositions according to the present invention have been developed for the oil & gas industry and its associated applications, by targeting the problems of corrosion, logistics & handling, human & environmental exposure, reaction rates, toxicity levels, biodegradation tendencies and formation/fluid compatibilities and facility and/or production and water treatment infrastructure operational compatibilities. It is an object of the present invention to provide a modified acid composition which can be used over a broad range of applications in the oil and gas industry and which exhibit advantageous properties over known compositions.
  • a method to improve and/or ensure the stability of an aqueous composition comprising an alkanolamine and HC1 where such a composition is typically saturated or a near saturated state.
  • the stability refers to the temperature stability.
  • the alkanolamine is selected from the group consisting of: monoethanolamine; diethanolamine and triethanolamine. The most preferred being monoethanolamine.
  • a premix composition also referred to as pre-blend
  • a commercial grade acid such as hydrochloric acid
  • a modified acid composition comprising: a strong acid and an alkanolamine in a molar ratio ranging from 3:1 to 15:1, preferably from 3:1 to 10:1; more preferably from 4:1 to 8:1, also preferably from 5:1 to 6.5:1.
  • a method to increase the stability of an aqueous composition comprising an alkanolamine, said method comprising the steps of: providing a vessel; adding a pre-determined amount of water into said vessel; adding a pre-determined amount of an acid to said water; and adding said alkanolamine to said vessel; and mixing the blend until resulting mixture is homogeneous; wherein the resulting mixture of alkanolamine and said acid has a pH ranging from 7 to 11 , is stable down to a temperature of -5°C and said resulting mixture comprises said alkanolamine and HC1 in a molar ratio ranging from 1:1 to 1:0.1 of alkanolamine: acid.
  • the resulting aqueous composition comprising said alkanolamine and acid in a molar ratio ranging from 1:1 to 1:0.2 of alkanolamine: acid.
  • the resulting aqueous composition comprising said alkanolamine and acid in a molar ratio ranging from 1:1 to 1:0.4 of alkanolamine:acid.
  • resulting aqueous composition comprising said alkanolamine and acid in a molar ratio ranging from 1:1 to 1:0.6 of alkanolamine: acid.
  • the acid is selected from the group consisting of: organic acids; mineral acids; and combinations thereof.
  • the organic acid is selected from the group consisting of: citric acid; acetic acid; and the like.
  • the mineral acid is selected from the group consisting of: HC1; nitric acid; sulfuric acid; and the like. More preferably, the mineral acid is HC1.
  • the alkanolamine is selected from the group consisting of: monoethanolamine; diethanolamine; and triethanolamine.
  • a stabilized aqueous composition of alkanolamine-acid wherein said composition consists of:
  • an alkanolamine present in an amount ranging from 9 wt.% to 15 wt.%.
  • composition has a pH ranging from 7 to 11 and is stable down to a temperature of -5°C, wherein stable is meant to understand that the alkanolamine does not precipitate out from the composition.
  • said alkanolamine is present in an amount ranging from 10 wt.% to 13 wt.%.
  • said alkanolamine is present in an amount ranging from 10.5 wt.% to 12 wt.%.
  • a stabilized aqueous composition of an alkanolamine for the preparation of a reconstituted modified acid composition, wherein said stabilized aqueous composition of alkanolamine consists of:
  • said alkanolamine in an amount ranging from 9 wt.% to 15 wt.%;
  • said stabilized aqueous composition of alkanolamine has a pH of no more than 10.0 and is stable down to a temperature of -10°C, wherein stable is meant to understand that the alkanolamine does not recrystallize out from the composition; and wherein said reconstituted modified acid composition has a pH below 1 and comprises said alkanolamine and HC1 in a molar ratio ranging from 1:3 to 1:15.
  • a method of preparing a reconstituted modified acid composition comprising an alkanolamine and an acid, said method comprising the steps of: providing a vessel; adding a pre-determined amount of water into said vessel; adding a pre-determined amount of a first acid to said water; and adding an alkanolamine to said vessel; and mixing the blend until resulting mixture comprising said alkanolamine and said first acid is homogeneous; wherein the resulting aqueous composition of alkanolamine and said first acid has a pH ranging from 7 to 11, is stable down to a temperature of -5°C and said resulting mixture comprises said alkanolamine and said first acid in a molar ratio ranging from 1:1 to 1:0.1 of alkanolamine:acid; providing a predetermined amount of mineral acid such as HC1; nitric acid; sulfuric acid; and the like; admixing said mineral acid with said resulting aqueous composition comprising said alkanolamine and
  • Preferred embodiments of the present invention provide a modified acid composition which, upon proper use, results in a very low corrosion rate on oil and gas industry tubulars down-hole tools and equipment.
  • a modified acid composition for use in the oil industry which is biodegradable.
  • a modified acid composition for use in the oil industry which will provide a thermal stability at temperatures above 90°C and up to 190°C.
  • an aqueous modified acid composition for use in the oil industry which affords corrosion protection at an acceptable oilfield limit at temperatures ranging up to 190°C.
  • an aqueous modified acid composition for use in the oil industry which has minimal exothermic reactivity upon dilution or during the dilution process with water.
  • a method to maintain the stability of an alkanolamine solution (especially during shipping or long term storage) prior to its combination in a vessel or on-the-fly (OTF) with hydrochloric acid to provide a reconstituted modified acid composition for use in oil and gas activities.
  • the stability refers to temperature stability where, conventionally, an alkanolamine solution would precipitate at temperatures below +10°C.
  • said composition can be used to reconstitute a modified acid, where said modified acid comprises: - an alkanolamine & hydrogen chloride in a molar ratio ranging from 1:2.1 to 1:12.5; more preferably, said alkanolamine and hydrogen chloride are present in a molar ratio ranging from 1 :3 to 1 : 12.5 ; even more preferably said alkanolamine and HC1 are present in a molar ratio ranging from 1:3.5 to 1:9; yet even more preferably in a molar ratio ranging from 1:4.5 to 1:8.5; and yet even more preferably in a molar ratio ranging from more than 1:5 to 1:6.5.
  • said modified acid comprises: - an alkanolamine & hydrogen chloride in a molar ratio ranging from 1:2.1 to 1:12.5; more preferably, said alkanolamine and hydrogen chloride are present in a molar ratio ranging from 1 :3 to 1 : 12.5 ; even more preferably said alkan
  • a process to stabilize a saturated or near saturated aqueous alkanolamine solution when such is exposed to temperatures below 0°C The inventors have noticed that an alkanolamine solution as a premix (also referred to as preblend) for the preparation of a modified acid comprising HC1 and an alkanolamine is being shipped to a destination prior to mixing this alkanolamine composition with commercial grade mineral acid, preferably HC1 (such as but not limited to 32% HC1, 37% HC1) would sometimes exhibit some issues of stability.
  • HC1 such as but not limited to 32% HC1, 37% HC1
  • the inventors have surprisingly discovered that by adding up to 1% wt/wt of an acid (such as, but not limited to HC1) into a saturated alkanolamine (such as monoethanolamine), they could enhance the stability of such a solution and subsequently ensure that the monoethanol amine would not reprecipitate out of solution during the time it was exposed to conditions which typically cause the precipitation of the alkanolamine.
  • an acid such as, but not limited to HC1
  • a saturated alkanolamine such as monoethanolamine
  • the resulting reconstituted modified acid composition will, upon proper use, results in a very low corrosion rate on oil and gas industry tubulars and equipment compared to mineral acids, such as HC1.
  • the reconstituted alkanolamine-HCl- containing modified acid composition can be used in the oil industry and is biodegradable.
  • the reconstituted alkanolamine-HCl- containing modified acid composition can be used in the oil industry as it possesses a controlled, more methodical spending (reacting) nature that is near linear as temperature increases, low-fuming/vapor pressure, low- toxicity, and has a highly controlled manufacturing process ensuring consistent end product strength and quality.
  • a reconstituted aqueous modified acid composition for use in the oil industry which has a pH below 1.
  • a reconstituted aqueous modified acid composition for use in the oil industry which will keep iron particles and solubilized carbonate in solution even as the pH rises to a level > 4 pH.
  • a reconstituted aqueous modified acid composition for use in the oil industry which will provide a thermal stability at temperatures above 100°C.
  • a reconstituted modified acid composition for use in the oil industry which will provide corrosion protection at an acceptable oilfield limit when said composition is in contact with metal components and is at temperatures ranging from 100°C to 220°C.
  • a reconstituted synthetic acid composition for use in the oil industry which has minimal exothermic reactivity upon dilution or during the reaction process.
  • the reconstituted aqueous modified acid composition for use in the oil industry is compatible with existing industry acid additives.
  • an aqueous synthetic acid composition for use in the oil industry which has higher salinity tolerance.
  • a tolerance for high salinity fluids, or brines, is desirable for onshore and offshore acid applications.
  • Conventional acids are normally blended with fresh water and additives, typically far offsite, and then transported to the area of treatment as a finished blend. It is advantageous to have an alternative that can be transported as a concentrate safely to the treatment area, then blended with a saline produced water or sea water greatly reducing the logistics requirement.
  • a conventional acid system can precipitate salts/minerals heavily if blended with fluids of an excessive saline level resulting in formation plugging or ancillary damage, inhibiting production and substantially increasing costs.
  • Brines are also typically present in formations, thus having an acid system that has a high tolerance for brines greatly reduces the potential for formation damage or emulsions forming down-hole during or after product placement/spending (reaction) occurs.
  • an aqueous synthetic acid composition for use in the oil industry which is immediately reactive upon contact/application.
  • an aqueous synthetic acid composition for use in the oil industry which results in less unintended near wellbore erosion or face dissolution due to a more controlled reaction rate. This, in turn, results in deeper formation penetration, increased permeability, and reduces the potential for zonal communication during a typical 'open hole' mechanical isolation application treatment.
  • a highly reactive acid such as hydrochloric acid
  • hydrochloric acid is deployed into a well that has open hole packers for isolation (without casing) there is a potential to cause a loss of near-wellbore compressive strength resulting in communication between zones or sections of interest as well as potential sand production, and fines migration.
  • an aqueous synthetic acid composition for use in the oil industry which provides a controlled and comprehensive reaction rate throughout a broad range of temperatures up to 220°C.
  • the reconstituted MEA-HC1- containing modified acid composition can be used in a molar ratio ranging from 1 :3.5 to 1 : 12.5 for injection into an oil or gas well to perform a treatment with said composition; recovering the spent acid from the well; and sending the spent acid to a plant.
  • the reconstituted MEA-HC1- containing modified acid composition can be used to overcome many of the drawbacks found in the use of compositions of the prior art related to the oil & gas industry.
  • the reconstituted MEA-HC1- containing modified acid composition can be used in a method of matrix acidizing a hydrocarbon- containing dolomite formation, said method comprising: - providing a composition comprising a HC1 and MEA mixture and water; wherein the molar ratio between the HC1 and the MEA ranges from 4.5:1 to 8.5:1, - injecting said composition downhole into said formation at a pressure below the fracking pressure of the formation; and - allowing a sufficient period of time for the composition to contact said formation to create wormholes in said formation.
  • the reconstituted MEA-HC1- containing modified acid composition can be used in the oil industry to perform an activity selected from the group consisting of: stimulate formations; assist in reducing breakdown pressures during downhole pumping operations; treat wellbore filter cake post drilling operations; assist in freeing stuck pipe; descale pipelines and/or production wells; increase injectivity of injection wells; lower the pH of a fluid; remove undesirable scale on a surface selected from the group consisting of: equipment, wells and related equipment and facilities; fracture wells; complete matrix stimulations; conduct annular and bullhead squeezes & soaks; pickle tubing, pipe and/or coiled tubing; increase effective permeability of formations; reduce or remove wellbore damage; clean perforations; and solubilize limestone, dolomite, calcite and combinations thereof; said reconstituted modified acid comprises: an alkanolamine & hydrogen chloride in a molar ratio ranging from 1:2.1 to 1:12.5; more preferably, said alkanol
  • a precursor also referred to as a premix or pre-blend
  • a synthetic or modified acid composition comprising: a strong acid and an alkanolamine in a molar ratio of not more than 15:1; preferably in a molar ratio not more than 10:1, more preferably in a molar ratio of not more than 8:1; even more preferably in a molar ratio of not more than 5:1; yet even more preferably in a molar ratio of not more than 4.1:1; and yet even more preferably in a molar ratio of not less than 3:1.
  • the main components in terms of volume and weight percent of the composition of the present invention comprise an alkanolamine and a strong acid, such as HC1, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid.
  • a preferred strong acid is HC1.
  • An alkanolamine according to the present invention contains at least one amino group, -NH2, and one alcohol group, -OH.
  • Preferred alkanolamines according to the present invention include, but are not limited to, monoethanolamine, diethanolamine and triethanolamine. More preferred are monoethanolamine, diethanolamine. Most preferred is monoethanolamine.
  • a Lewis acid/base adduct When added to hydrochloric acid a Lewis acid/base adduct is formed where the primary amino group acts as a Lewis base and the proton of the HC1 as Lewis acid.
  • the formed adduct greatly reduces the hazardous effects of the hydrochloric acid on its own, such as the fuming/vapor pressure effect, the hygroscopicity, and the highly corrosive nature.
  • the molar ratio of the two main components can be adjusted or determined depending on the intended application and the desired solubilizing ability. While a molar ratio of HC1:MEA of 1:1 can be used, results are significantly optimized when working above a 2:1 ratio and preferably above a 3:1 ratio.
  • the strong acid is HC1
  • an alkanolamine such as monoethanolamine is a compound known by the person of ordinary skill in the art, the latter knows that such a compound is not to be mixed with a strong acid such as HC1.
  • the person skilled in the art will note upon review of the DOW safety data sheet for monoethanolamine LFG 85 that it indicates that one must avoid contact of this compound with strong acids.
  • Various corrosion inhibitors can be incorporated into a preferred composition as disclosed herein which comprises a strong acid and an alkanolamine to reduce corrosion on the steel which is contacted by the reconstituted composition according to the present invention.
  • the reconstituted composition may further comprise organic compounds which may act as corrosion inhibitors selected from the group consisting of: acetylenic alcohols, aromatic or aliphatic aldehydes (e.g.
  • aldehydes a.p -unsaturated aldehydes
  • alkylphenones amines, amides, nitrogen-containing heterocycles (e.g. imidazoline-based), iminium salts, triazoles, pyridine and its derivatives or salts, quinoline derivatives, thiourea derivatives, thiosemicarbazides, thiocyanates, quaternary amine salts, and condensation products of carbonyls and amines.
  • Intensifiers which can be incorporated into compositions according to the present invention are selected from the group consisting of: formic acid, potassium iodide, antimony oxide, copper iodide, sodium iodide, lithium iodide, aluminium chloride, bismuth oxide, calcium chloride, magnesium chloride and combinations of these.
  • an iodide compound such as potassium iodide is used.
  • Other additives can be optionally added to a composition according to a preferred embodiment of the present invention.
  • a non-limiting list of such common additives includes iron control agents (e.g. reducing agents), water-wetting surfactants, non-emulsifiers, de-emulsifiers, foaming agents, antisludging agents, clay and/or fines stabilizer, scale inhibitors, mutual solvents, friction reducer.
  • the alkanolamine-HCl ratio in the reconstituted modified acid composition it is possible to adjust the alkanolamine-HCl ratio in the reconstituted modified acid composition depending on the intended application and the desired solubilizing ability.
  • the solubilizing ability will increase while still providing certain health, safety, environmental and operational advantages over hydrochloric acid.
  • the alkanolamine at a molar ratio less than 1 : 1 to the moles of HC1 acid (or any acid).
  • the reconstituted composition according to the present invention comprises at most 1 mole of alkanolamine per 3.0 moles of HC1.
  • the alkanolamine allows for a reduced rate of reaction when in the presence of carbonate-based materials. This again is due to the stronger molecular bonds associated over what hydrochloric acid traditionally displays.
  • the composition according to the present invention is mainly comprised of MEA (which is biodegradable)
  • the product testing has shown that the MEA will maintain the same biodegradability function, something that hydrochloric acid will not on its own.
  • Typical ship tanks which are used to carry chemicals are coated with acid-resistant coatings.
  • One widely-used type of coating is epoxy-based. Appropriate epoxy-cased coatings will protect both the steel of the from being affected by the contents and the contents from being contaminated.
  • One such epoxy -based coating used for such purpose is Hempadur® 35760. This coating provides very high corrosion protection properties and excellent chemical resistance and, is especially well-suited for new and old storage tanks containing oils, fuels, bio fuels and a wide range of chemicals.
  • Another epoxy-based coating is Hempadur® 85671, an epoxy phenolic resistant to very aggressive cargos, such as acids.
  • Intershield® 300HS Another type of coating is Intershield® 300HS which is described as a high solids, abrasion resistant, aluminum pure epoxy coating capable of providing excellent long term anti -corrosive protection and low temperature capability. It comes as a universal primer which can be applied directly to mechanically prepared shop primer or suitably prepared bare steel.
  • such blending is intended on yielding a reconstituted modified acid composition
  • a reconstituted modified acid composition comprising an alkanolamine and HC1 in a molar ratio ranging from 1:3 to 1:12.5; preferably in a molar ratio ranging from 1:4.5 to 1:9, and more preferably in a molar ratio ranging from more than 1:5 to 1:8.5.
  • the composition comprises alkanolamine and HC1 in a molar ratio ranging from 1:4.5 to 1:8.5.
  • Example 1 Preparation of a composition according to a preferred embodiment of the present invention
  • a reconstituted modified acid comprising an alkanolamine and HC1, which both component can be transported on a ship, one first determines the amount of alkanolamine which can be put into the water tank portion of the ship.
  • the other component of the reconstituted modified acid, the HC1 is typically found in the acid tank portion of the ship and thus requires no calculation.
  • Table 1 indicates the components as well as their amounts in a reconstituted modified acid comprising an alkanolamine and HC1 according to a preferred embodiment of the present invention.
  • Table 2 provides a list of specifications for the reconstituted acid according to a preferred embodiment of the present invention obtained from the example listed in Table 1.
  • Table 1 Components and amounts to prepare a reconstituted modified acid comprising an alkanolamine and HC1
  • the number of moles of MEA per kg of reconstituted modified acid is obtained as follows:
  • the components and the amounts required to prepare a pre-blend for such a reconstituted modified acid is listed in Table 3.
  • the final pH of the pre -blend is measured to be 7.19.
  • Table 4 provides a list of specifications for the pre -blend according to a preferred embodiment of the present invention
  • Table 3 Components and amounts to prepare a pre-blend to use in preparing a reconstituted modified acid comprising an alkanolamine and HC1
  • Table 4 Specification for a pre-blend according to a preferred embodiment of the present invention as set out in Table 3
  • Table 5 Specification for the reconstituted acid made using a pre-blend according to a preferred embodiment of the present invention
  • the above pre -blend can then be mixed on-the-fly with 392.31 g of 36% HC1 to obtain a kilogram of reconstituted modified acid for use in various oil and gas field operations as described herein.
  • Table 6 Components and amounts to prepare various pre-blends (each having a different pH) to use in preparing a reconstituted modified acid comprising an alkanolamine and HC1
  • each one of the pre -blends can then be mixed on-the-fly with 392.03 g of 36% HC1 to obtain a reconstituted modified acid for use in various oil and gas field operations as described herein.
  • the Intershield® 300HS epoxy was prepared by mixing 2.5 parts of A with 1 part of B as per manufacturers specifications.
  • the 316SS coupons were then coated in the epoxy and hung to allow excess to drip off.
  • the coupons were then placed into an oven at 45 °C (113 °F) for 1 hour and then removed to apply a second layer of epoxy coat to cover any areas that may have had a thin layer or exposed comers.
  • the coupons were then hung to dry overnight in an oven set to 45 °C (113 °F) before the coupons were weighed. A photo of each coupon was taken to document the initial appearance of the surface.
  • each blend was evaluated at ambient temperature, approximately 20°C (68°F) and at 50°C (122°F) on the epoxy coated coupons.
  • the tests were executed on a bench top, while at 50°C (122°F), tests were executed in a heated water bath.
  • the coupons were removed, washed with warm water and soap, iso-propanol, and dried.
  • the weights of the coated coupons were recorded.
  • a photo of each coupon was taken to document the appearance of the surface after the exposure to the Pre -blend #6 and Pre-blend #7. Test results of the compatibility experiment with Intershield® 300HS epoxy coated coupons are shown in Table 8.
  • the Hempadur® 85671 epoxy was prepared by mixing 8.9 parts of A with 1.1 parts of B as per manufacturers specifications.
  • the 316SS coupons were then coated in the epoxy and hung to allow excess to drip off.
  • the coupons were then placed into an oven at 45 °C (113 °F) for 1 hour and then removed to apply a second layer of epoxy coat to cover any areas that may have had a thin layer or exposed comers.
  • the coupon was then hung to dry overnight in an oven set to 45 °C (113 °F) before the coupons were weighed. A photo of each coupon was taken to document the initial appearance of the surface.
  • each blend was evaluated at ambient temperature, approximately 20°C (68°F) and at 50°C (122°F) on the epoxy coated coupons.
  • the tests were executed on a bench top, while at 50°C (12°F), tests were executed in a heated water bath. After the exposure time, the coupons were removed, washed with warm water and soap, iso-propanol, and dried. The weights of the coated coupons were recorded. A photo of each coupon was taken to document the appearance of the surface after the exposure to the Pre -blend #6 and Pre-blend #7. Test results of the compatibility experiment with Hempadur® 85671epoxy-coated coupons are shown in Table 9.
  • Corrosion testing was performed utilizing a composition comprising MEA:HC1 in a molar ratio of 1:5.5 (hereinafter referred to as reconstituted modified acid 1:5.5).
  • This composition was prepared by blending pre-blend #6 (neutral pH), 36% HC1 and CI-9CNE.
  • the resulting modified acid composition was exposed to a stainless steel (316SS) coupon at a temperature of 110°C (230°F).
  • the corrosion testing was performed at a 33 % concentration of the above referred to MEA-HC1 composition comprising MEA:HC1 in a molar ratio of 1:5.5 for a testing period of 6 hours.
  • the corrosion testing results are found in Table 10.
  • CI-9CNE is a corrosion inhibitor comprising a non-emulsifier.
  • Corrosion tests were executed in a high pressure/high temperature Teflon lined cell.
  • the coupon was washed with acetone, air dried, and weighed, before being suspended in the test fluid and then the cell was pressurized with nitrogen.
  • Each cell was placed in a preheated oven for the specified test duration, plus an additional 30 minutes of heat up time for tests less than 24 hours in duration. After the exposure period, each cell was depressurized, and the coupon was removed, washed with water, followed by an acetone wash, air dried, and then weighed.
  • the pitting index indicates: No pits.
  • the surface is the same as for the original untreated coupon. This is from the pitting index reported in: Finsgar, M.; Jackson, J. Corrosion Science, 2014, 86, 17-41
  • the corrosion rate was determined from the weight loss, and the pitting index was evaluated visually at 40X magnification and compared to the literature, and a photo of the coupon surface at 10X and 40X magnification was taken.
  • the resulting composition is a clear (slightly yellow) liquid having shelf-life of greater than 1 year. It has a boiling point temperature of approximately 100°C. It has a specific gravity of 1.1 ⁇ 0.02. It is completely soluble in water and its pH is less than 1. The freezing point was determined to be less than - 35°C.
  • the organic component in the composition is biodegradable.
  • the composition is classified as a mild irritant according to the classifications for skin tests.
  • the composition is substantially lower fuming compared to 15% HC1.
  • composition thus prepared was also tested for skin corrosiveness and deemed non-corrosive to the skin.
  • Oral toxicity was calculated using the LD50 rat model and deemed to be of low oral toxicity. It is considered readily biodegradable and offers a lower bioaccumulative potential when compared to 15%
  • Canadian Patent 3,006,476 discloses the dermal safety data for modified acid composition comprising an alkanolamine (such as MEA) and HC1 in various molar ratios.
  • the patent also discloses the scale solubility and dissolution power of such compositions, the disclosure in CA 3,006,476 is hereby incorporated in its entirety.
  • These compositions are similar to the reconstituted alkanolamine-HCl- containing modified acid composition (such as, but not limited to MEA-HC1) discussed herein.
  • the teachings of Canadian Patent 3,006,476 are hereby incorporated by reference.
  • modified acid composition comprising MEA and HC1 obtained from the mixing of an aqueous pre-blend containing monoethanolamine composition according to a preferred embodiment of the present invention with commercial grade HC1 to dissolve scale was assessed. It was determined that a reconstituted modified acid composition (obtained from the mixing of an aqueous pre-blend containing monoethanolamine composition according to a preferred embodiment of the present invention with commercial grade HC1) provides an excellent solubilizing ability when dealing with various oilfield scales. Its solubilizing ability is comparable to the solubility of most many mineral and organic acid packages typically utilized.
  • the uses (or applications) of the reconstituted modified acid composition comprising an alkanolamine (such as monoethanolamine, MEA) and HC1 according to the present invention upon dilution thereof ranging from approximately 1 to 90% dilution are listed below in Table 11 and include, but are not limited to: injection/disposal treatments; matrix acid squeezes, soaks or bullheads; acid fracturing, acid washes; fracturing spearheads (breakdowns); pipeline scale treatments, cement breakdowns or perforation cleaning; pH control; and de-scaling applications, high temperature (up to 180°C) cyclical steam scale treatments and steam assisted gravity drainage (SAGD) scale treatments (up to 220°C)
  • the methods of use generally comprise the following steps: providing a composition according to a preferred embodiment of the present; exposing a surface (such as a metal surface) to the acid composition; allowing the acid composition a sufficient period of time to act upon said surface; and optionally, removing the acid composition when
  • Another method of use comprises: injecting the acid composition into a well and allowing sufficient time for the acid composition to perform its desired function.
  • Yet another method according to the present invention comprises the steps of: providing a composition according to a preferred embodiment of the present; injecting the composition into a well; an optional step of dilution of the acid composition can be performed if deemed necessary prior to injection downhole; monitoring the various injection parameters to ensure that the pressure and rate of injection are below frac pressures and below conventional injection rates used for conventional acids such as HC1; allowing sufficient period of time to act upon said formation to obtain the desired wormholing effect; and optionally, removing the acid composition when the exposure time has been determined to be sufficient for the operation to be complete or sufficiently complete.
  • Yet another method of use comprises: exposing the acid composition to a body of fluid (typically water) requiring a decrease in the pH and allowing sufficient exposure time for the acid composition to lower the pH to the desired level.
  • a body of fluid typically water
  • the main advantages of the use of the synthetic acid composition included: the reduction of the total loads of acid, and the required number of tanks by delivering concentrated product to location and diluting with fluids available on location (with low to high salinity production water).
  • Other advantages of the composition according to the present invention include: operational efficiencies which lead to the elimination of having to periodically circulate tanks of HC1 acid due to chemical separation; reduced corrosion to downhole tubulars; ultra-high temperature corrosion protection up to 220°C, less facility disruptions due to iron pick up and precipitation, thermal stability of a synthetic acid, and reduced hazardous HC1 acid exposure to personnel and environment by having a non-low hazard, low fuming acid (lower vapour pressure) on location.
  • a synthetic acid composition according to a preferred embodiment of the present invention can be used to treat scale formation in SAGD operations at ultra-high temperatures (up to 220°C) while achieving acceptable corrosion limits set by industry. This also eliminates the need for the SAGD operation to be halted for a "cool down prior to a scale treatment and said synthetic acid is injected into said well to treat scale formation inside said well at high temperatures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne un procédé permettant d'augmenter la stabilité d'une composition aqueuse comprenant une alcanolamine, ledit procédé comprenant les étapes consistant à : mettre à disposition un récipient ; ajouter une quantité prédéfinie d'eau dans ledit récipient ; ajouter une quantité prédéfinie d'un acide à ladite eau ; et ajouter ladite alcanolamine audit récipient ; et mélanger le mélange jusqu'à ce que le mélange résultant soit homogène ; le mélange résultant d'alcanolamine et dudit acide ayant un pH allant de 7 à 11, étant stable jusqu'à une température de -5 °C et ledit mélange résultant comprenant ladite alcanolamine et HCl dans un rapport molaire allant de 1 : 1 à 1 : 0,1 d'alcanolamine : acide.
PCT/IB2023/054673 2022-05-06 2023-05-04 Pré-mélanges d'acides modifiés stabilisés WO2023214360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA3157830A CA3157830A1 (fr) 2022-05-06 2022-05-06 Premelanges d'acide modifie stabilise
CA3157830 2022-05-06

Publications (1)

Publication Number Publication Date
WO2023214360A1 true WO2023214360A1 (fr) 2023-11-09

Family

ID=88584771

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2023/054673 WO2023214360A1 (fr) 2022-05-06 2023-05-04 Pré-mélanges d'acides modifiés stabilisés

Country Status (2)

Country Link
CA (1) CA3157830A1 (fr)
WO (1) WO2023214360A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3095379A (en) * 1960-07-26 1963-06-25 Schwartz Hyman Metal cleaning compositions
US20150027347A1 (en) * 2012-02-06 2015-01-29 Chryso Set-accelerating admixture having improved stability
US11161808B1 (en) * 2020-09-09 2021-11-02 Vitaworks Ip, Llc Cyclic process for producing taurine from monoethanolamine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3095379A (en) * 1960-07-26 1963-06-25 Schwartz Hyman Metal cleaning compositions
US20150027347A1 (en) * 2012-02-06 2015-01-29 Chryso Set-accelerating admixture having improved stability
US11161808B1 (en) * 2020-09-09 2021-11-02 Vitaworks Ip, Llc Cyclic process for producing taurine from monoethanolamine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J H JONES: "Preparation of alkanolamine hydrochlorides", JOURNAL OF THE ASSOCIATION OF OFFICIAL AGRICULTURAL CHEMISTS, vol. 27, no. 3, 1 August 1944 (1944-08-01), US , pages 467 - 472, XP009550417, ISSN: 0095-9111, DOI: 10.1093/jaoac/27.3.467 *

Also Published As

Publication number Publication date
CA3157830A1 (fr) 2023-11-06

Similar Documents

Publication Publication Date Title
AU2022201199B2 (en) Lysine: hydrochloride synthetic acid compositions as alternatives to conventional acids in the oil and gas industry
AU2018276317B2 (en) Novel modified acid compositions as alternatives to conventional acids in the oil and gas industry
CA2892877A1 (fr) Utilisation de compositions d'acide synthetique non reglementees comme remplacement des acides conventionnels dans l'industrie du petrole et du gaz
CA2892876A1 (fr) Utilisation de compositions acides synthetiques comme solutions de rechange aux acides classiques dans l'industrie du petrole et du gaz
CA3134250A1 (fr) Nouveau pack anticorrosion
US20230272266A1 (en) Modified acid compositions
CA2961777C (fr) Compositions d'acides synthetiques utilisables comme substituts d'acides classiques dans l'industrie petroliere et gaziere
WO2023214360A1 (fr) Pré-mélanges d'acides modifiés stabilisés
CA2961787C (fr) Compositions d'acides synthetiques utilisables comme substituts d'acides classiques dans l'industrie petroliere et gaziere
US11725288B2 (en) Corrosion inhibition package
WO2023223261A1 (fr) Stabilisation de compositions aqueuses acides aminés-hcl
WO2023139538A1 (fr) Stabilisation de compositions aqueuses de lysine-hcl
US20170210980A1 (en) Synthetic acid compositions alternatives to conventional acids for use in the oil and gas industry

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23799366

Country of ref document: EP

Kind code of ref document: A1