WO2003062344A2 - Acidizing and scale treatment of subterranean formation - Google Patents
Acidizing and scale treatment of subterranean formation Download PDFInfo
- Publication number
- WO2003062344A2 WO2003062344A2 PCT/US2003/001891 US0301891W WO03062344A2 WO 2003062344 A2 WO2003062344 A2 WO 2003062344A2 US 0301891 W US0301891 W US 0301891W WO 03062344 A2 WO03062344 A2 WO 03062344A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- scale inhibitor
- phosphonates
- iron ions
- reducing agent
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
Classifications
-
- 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
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- 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
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Definitions
- This invention relates to the treatment of subterranean formations using acid and scale inhibitors.
- the invention involves a one-step process for acidizing and scale treatment of a formation.
- the second step consists of carrying out the squeeze operation with scale inhibitor. Another possibility is to treat the well sequentially by inserting pads of liquid between the HCI/spent acid and the fluids containing the scale inhibitor. These procedures are more expensive and result in more down time than a combined operation.
- the method of the present invention involves the steps of (a) injecting into a subterranean formation a treating solution of (i) an acid that reacts with downhole materials and equipment to form CaC12, and iron ions,
- Each of the three fluid components of the treating solution may be as follows:
- Acid Typical well treating acids include aqueous solution of 1 to 38% HC1 , with 15% HCI being preferred.
- Other acids include sulfamic acid hydrofluoric acid, acetic acid, formic acid, etc. and mixtures thereof.
- Scale inhibitor The preferred oil field scale inhibitors include phosphate esters, phosphonates, sulfonates, and polyacrylates. Other scale inhibitors include copolymers and terpolymers of acrylates, sulfonates and phosphonates, phosphinico polycarboxylie acids (PPCA) and mixtures thereof. Particularly useful scale inhibitors include 2- hydroxyethyl imino bis methylenc phosphonie acid, fatty amine phosphonates, triethanolamine phosphate ester, DETA phosphonatc
- TETA phosphonate hexaphosphonates
- the additive for preventing or inhibiting the formation of a precipitate of iron ions and the scale inhibitor may take a variety of forms such as chelating agents, or agents for maintaining the iron ions in the ferrous state,
- the preferred additive is a reducing agent for reducing
- Example reducing agents include ascorbic acid, citric acid and dioglycolic acid, oxalic acid, and erythorbic acid and mixtures thereof.
- the preferred reducing agent is erythorbic acid.
- the three water soluble or dispersible components may be used in one solution, or pumped in any sequence. It is preferred that they be used in one treating solution in the, following concentrations (wt.%):
- the treating fluid may be premixed ("hatched") or mixed continuously ("on the fly") during injection. All of the components may be blended together or they may be injected in any sequence of 1 , 2 and 3.
- the precipitate preventative e.g. reducing agent
- the amount of treating fluid squeezed into the formation will depend on several factors including the degree of scaling, the type of scale, length of perforations, etc. From 1 to 100 barrels per foot of perforations will be satisfactory for most treatments.
- the squeeze operation may be carried out with other work over procedures and may be in accordance with procedures well known in the art, including the use of corrosion inhibitors and other well treating chemicals.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
A one step squeeze treatment of a subterranean formation involves the treatment with a treating solution comprising an acid, a scale inhibitor, and a reducing agent. The presence of the reducing agent prevents the iron ions in the system from reacting with and forming a precipitate with the scale inhibitor and maintains the iron ions in the ferrous state.
Description
Acidizing and Scale Treatment of Subterranean Formation
FIELD OF INVENTION
This invention relates to the treatment of subterranean formations using acid and scale inhibitors. In a preferred aspect, the invention involves a one-step process for acidizing and scale treatment of a formation.
BACKGROUND OF THE INVENTION
The deposition of scale from boat produced and source waters is common in oil-producing operations. Depositions occur downhole and in flow lines, separators, and other surface facilities. Scale is a problem in acid/scale squeeze operations where iron is present as an impurity either in the water or the reaction product of the acid with scale or oil field equipment. The reaction of the impure iron with scale inhibitors may produce solids that damage the formation or block production equipment. Because of the precipitation resulting from the mixing of the incompatible fluids, present procedures generally require two separate operations for wells that need both well work ovens (e.g. acidizing) and scale squeezes. With two separate operations, the well is first treated with concentrated HCI, and the resulting spent acid is cleared out of the well. The second step consists of carrying out the squeeze operation with scale inhibitor, Another possibility is to treat the well sequentially by inserting pads of liquid between the HCI/spent acid and the fluids containing the scale inhibitor. These procedures are more expensive and result in more down time than a combined operation.
SUMMARY OF THE INVENTION
The method of the present invention involves the steps of (a) injecting into a subterranean formation a treating solution of (i) an acid that reacts with downhole materials and equipment to form CaC12, and iron ions,
(ii) a scale inhibitor, and
(iii) an additive capable of preventing the scale inhibitor from forming a precipitate with iron ions; and (b) after a suitable shut in time, producing fluid from the well.
Each of the three fluid components of the treating solution may be as follows:
(1 ) Acid: Typical well treating acids include aqueous solution of 1 to 38% HC1 , with 15% HCI being preferred. Other acids include sulfamic acid hydrofluoric acid, acetic acid, formic acid, etc. and mixtures thereof.
(2) Scale inhibitor: The preferred oil field scale inhibitors include phosphate esters, phosphonates, sulfonates, and polyacrylates. Other scale inhibitors include copolymers and terpolymers of acrylates, sulfonates and phosphonates, phosphinico polycarboxylie acids (PPCA) and mixtures thereof. Particularly useful scale inhibitors include 2- hydroxyethyl imino bis methylenc phosphonie acid, fatty amine phosphonates, triethanolamine phosphate ester, DETA phosphonatc
(pentaphosphonates) and TETA phosphonate (hexaphosphonates).
(3) The additive for preventing or inhibiting the formation of a precipitate of iron ions and the scale inhibitor may take a variety of forms such as chelating agents, or agents for maintaining the iron ions in the ferrous state, The preferred additive, however, is a reducing agent for reducing
Fe+++ to Fe++.
Example reducing agents include ascorbic acid, citric acid and dioglycolic acid, oxalic acid, and erythorbic acid and mixtures thereof.
The preferred reducing agent is erythorbic acid.
The three water soluble or dispersible components may be used in one solution, or pumped in any sequence. It is preferred that they be used in one treating solution in the, following concentrations (wt.%):
In the oil field squeeze operation, the treating fluid may be premixed ("hatched") or mixed continuously ("on the fly") during injection. All of the components may be blended together or they may be injected in any sequence of 1 , 2 and 3.
(1 ) injection of a solution HCI
(2) addition of reducing agent
(2) injection of 'the scale inhibitor solution
In either process, the precipitate preventative (e.g. reducing agent) reacts with the iron ions so that upon contact with the scale inhibitor, no precipitate is formed. The amount of treating fluid squeezed into the formation will depend on several factors including the degree of scaling, the type of scale, length of perforations, etc. From 1 to 100 barrels per foot of perforations will be satisfactory for most treatments.
The squeeze operation may be carried out with other work over procedures and may be in accordance with procedures well known in the art, including the use of corrosion inhibitors and other well treating chemicals.
Once the well is returned to production chemicals squeezed into the formation will slowly be produced along with well fluids and will treat the well.
Examples
Bottle tests carried out at 180°F to determine the compatibility of HCI or solutions and scaling agents with and without the precipitate preventative (e.g. reducing agent). The following aqueous solutions were prepared:
Sample Ingredients
Tests were ran by adding 0.6 wt.% erythorbic acid (reducing agent) to
Samples B, C, and D, followed by the addition of 3.5 wt.% of a scale inhibitor. The samples were observed for a precipitate. Comparison tests were rata on Samples B, C, D without the addition of the erythorbic acid. Table I presents the results. The tests on Sample D demonstrate the effectiveness of the presence of the reducing agent with the first 5 scale inhibitors tested.
Table I
Sni ipJe B
Scale Inhibitor No EA With EA Without EA With EA Without EA With EA Without EA
2-hydroxyethyl imino bis Not mo OK OK Not run OK OK Cloudy/ppt methylene phosphonic acid
Fatty Amine phospbonate Not run Cloudy/ppt (1) OK Not run OK OK CJoudy/ppt (2) tricthanolamine phosphate ester Not run OK OK Not run OK (4) OK Cloudy/ppt
DETA phospbonate (pentaphαsphonate) Not run Cloudy/ppt (I) Cloudy/ppt Not run OK (3) OK(?) Coundy/ppt
BMHT phosphonate Not run OK Cloudy/ppt Not run OK Cloudy/ppt (1) Cloudy/ppt
EDA phosphonate OK Cioudy/ppt (I) Cloudy/ppt Not run Cloudy/ppt Cloudy/ppt Cloudy/ppt polyvinylsulfonace Not run Not run OK Not run OK Not run OK poJyacrylic act J OK oκ- OK Cloudy/ppt (5) Cloudy/ppt Not run Not run
EA = Erythorbic Acid
1 = starts cloudy -> slight ppt starts after 1 hour, clear at 180 °F
2 = slightly cloudy
? = slightly cloudy -> clears
3 = immediate ppt goes into solution on soaking
4 = formed gel on heating
5 = small amount of ppt on heating-
6 = ppt formed soon after starting, did not go back into solution at 180 "F
Claims
1 . In a method of treating a subterranean formation with a treating solution containing acid and iron ions, the improvement wherein the treating solution further contains
(a) a scale inhibitor, and
(b) an additive capable of preventing or inhibiting the iron ions from forming a precipitate with the sole inhibitor.
2. The method of claim I wherein the iron ions enter the treating solution by the acid reacting with downhole equipment or materials.
3. The method of claim 1 wherein the acid is HCI.
4. The method of claim 3 wherein the additive is a reducing agent for reducing the iron ions to the ferrous state.
5. The method of claim 4 wherein the reducing agent is erythorbic acid.
6. The method of claim 4 wherein the scale inhibitor is selected from the group consisting of phosphonates, phosphate esters, polyacrylates, sulfonates, copolymers and terpolymers of aerylates, sulfonates and phosphonates, phosphinico polycarboxylic acid.
7. A method of treating a subterranean formation comprising the steps of (a) mixing an aqueous solution of
(i) HO,
(ii) a scale .inhibitor, and
(iii) an additive for preventing or inhibiting the scale inhibitor from forming a precipitate with any iron ions in the water, (b) injecting the treating solution into the formation whereby the reaction of the HCI with downhole equipment or materials forms iron ions and whereby the presence of an effective amount of the additive (iii) inhibits the iron ions from reacting with and forming a precipitate with the scale inhibitor.
8. The method of claim 7 wherein the HCI is present in a concentration of 1 to 38%.
9. The method of claim 7 wherein the scale inhibitor is selected from the group consisting of phosphonates, phosphate esters, and polyacrylic acid.
10. The method of claim 7 wherein the scale inhibitor i5 selected from the group consisting of phosphonates, phosphate esters, polyacrylates, sulfonates, copolymers and terpolymers of acrylates, sulfonates and phosphonates, phosphinico polycarboxylic acid, phosphoric acid and salts thereof and is present in the treating solution at a concentration of between 0.5 and 50 wt.%.
11. The method of claim 7 wherein the additive is a reducing agent and is present in the treating solution at a concentration of between 0.05 and 30 wt. %.
12. The method of claim 11 wherein the reducing agent is selected from the group consisting of erythorbic acid, ascorbic acid, citric acid, thioglycolic acid, oxalic acid and mixtures thereof.
13. An aqueous solution for treating a subterranean formation which comprises: (a) From 5 to 28 wt. 5b HO,
(b) From 0.5 to 10 wt_% of a scale inhibitor, and
(c) From 0.05 to 5 wt.% of a reducing agent for maintaining any iron in the treating solution in the ferrous state.
14. The treating solution of claim 13 wherein the scale inhibitor consisting of phosphonates, phosphate esters, polyacrylates, sulfonates, copolymers and terpolymers of acrylates, sulfonates and phosphonates, pbosphinico polycarboxylic acid.
15. The treating solution of claim 13 wherein the reducing agent is erythorbic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003217235A AU2003217235A1 (en) | 2002-01-22 | 2003-01-22 | Acidizing and scale treatment of subterranean formation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/055,823 | 2002-01-22 | ||
| US10/055,823 US20030150613A1 (en) | 2002-01-22 | 2002-01-22 | Acidizing and scale treatment of subterranean formation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2003062344A2 true WO2003062344A2 (en) | 2003-07-31 |
| WO2003062344A3 WO2003062344A3 (en) | 2004-04-08 |
Family
ID=27609227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2003/001891 Ceased WO2003062344A2 (en) | 2002-01-22 | 2003-01-22 | Acidizing and scale treatment of subterranean formation |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20030150613A1 (en) |
| AU (1) | AU2003217235A1 (en) |
| WO (1) | WO2003062344A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009002555A1 (en) | 2008-04-22 | 2009-10-29 | Basf Se | Use of complexing agents for the prevention of asphaltene and/or naphthenate-precipitation from crude oil, comprising oil-soluble, divalent complexing agent |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7081438B2 (en) * | 2003-08-13 | 2006-07-25 | Brine -Add Fluids Ltd. | Drilling fluids, drilling fluids additives and methods useful for limiting tar sands accretion on metal surfaces |
| US7611588B2 (en) * | 2004-11-30 | 2009-11-03 | Ecolab Inc. | Methods and compositions for removing metal oxides |
| US7703530B2 (en) * | 2005-08-10 | 2010-04-27 | Schlumberger Technology Corporation | Scale inhibitors compatible with sandstone acidizing |
| US20090104358A1 (en) * | 2007-10-17 | 2009-04-23 | Jacam Chemicals, Llc | Corrosion and scale inhibition compositions and methods of use thereof |
| US7841411B2 (en) * | 2007-12-14 | 2010-11-30 | Schlumberger Technology Corporation | Use of polyimides in treating subterranean formations |
| US7994102B2 (en) * | 2008-04-01 | 2011-08-09 | Baker Hughes Incorporated | Method of treating an alloy surface with an alkyl sarcosinate |
| US8967275B2 (en) * | 2011-11-11 | 2015-03-03 | Baker Hughes Incorporated | Agents for enhanced degradation of controlled electrolytic material |
| WO2015026325A1 (en) * | 2013-08-20 | 2015-02-26 | Halliburton Energy Services, Inc. | Methods and systems for iron control using a phosphinated carboxylic acid polymer |
| US20150368544A1 (en) * | 2014-06-24 | 2015-12-24 | Schlumberger Norge As | Methods of inhibiting salt precipitation and corrosion |
| US10081758B2 (en) | 2015-12-04 | 2018-09-25 | Ecolab Usa Inc. | Controlled release solid scale inhibitors |
| CA3024478A1 (en) | 2016-05-16 | 2017-11-23 | Ecolab Usa Inc. | Slow-release scale inhibiting compositions |
| WO2018118762A1 (en) | 2016-12-23 | 2018-06-28 | Ecolab Usa Inc. | Controlled release solid scale inhibitors |
| US11952534B2 (en) | 2019-12-30 | 2024-04-09 | Petróbras Brasileiro S. A.—Petrobras | Method for the combined application of scale remover and inhibitor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3633672A (en) * | 1970-05-11 | 1972-01-11 | Dow Chemical Co | Inhibition of deposition of scale |
| US3724544A (en) * | 1971-06-21 | 1973-04-03 | Texaco Inc | Secondary recovery method |
| US6192987B1 (en) * | 1999-04-06 | 2001-02-27 | Halliburton Energy Services, Inc. | Metal corrosion inhibitors, inhibited acid compositions and methods |
| US6436154B1 (en) * | 2000-09-28 | 2002-08-20 | Fmc Wyoming Corporation | Use of dodecylbenzene sulfonic acid or salt as a scale inhibitor |
-
2002
- 2002-01-22 US US10/055,823 patent/US20030150613A1/en not_active Abandoned
-
2003
- 2003-01-22 AU AU2003217235A patent/AU2003217235A1/en not_active Abandoned
- 2003-01-22 WO PCT/US2003/001891 patent/WO2003062344A2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009002555A1 (en) | 2008-04-22 | 2009-10-29 | Basf Se | Use of complexing agents for the prevention of asphaltene and/or naphthenate-precipitation from crude oil, comprising oil-soluble, divalent complexing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030150613A1 (en) | 2003-08-14 |
| AU2003217235A1 (en) | 2003-09-02 |
| WO2003062344A3 (en) | 2004-04-08 |
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