GB2423099A - Phosphorus containing species in sludge control - Google Patents
Phosphorus containing species in sludge control Download PDFInfo
- Publication number
- GB2423099A GB2423099A GB0502762A GB0502762A GB2423099A GB 2423099 A GB2423099 A GB 2423099A GB 0502762 A GB0502762 A GB 0502762A GB 0502762 A GB0502762 A GB 0502762A GB 2423099 A GB2423099 A GB 2423099A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphonic acid
- ester
- aminophosphonate
- stimulation fluid
- alkylated
- 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.)
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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
- C09K8/60—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
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method is provided for controlling the formation of ferric-ion-induced sludge in a process for the extraction of crude oil under acidic stimulation conditions. The method comprises the addition to the stimulation fluid or the formulation fluids of an effective amount of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate.
Description
PHOSPHORUS CONTAINING SPECIES IN SLUDGE CONTROL
This invention relates to a method for controlling, and preferably substantially preventing, the formation of ferric-ion-induced sludge in a process for the extraction of crude oil and to the use of a phosphorus containing species to break down already formed sludge.
In the extraction of crude oil, stimulation fluids which include acids (especially hydrochloric acid) are frequently used. The action of the acid on pipelines and reservoir rock causes dissolution of iron (as ferric ions) into the fluids. Under acidic conditions, the ferric ions cross-link high molecular weight organic molecules, such as asphaltenic and naphthenate molecules present in the oil, causing a thick sludge to be formed.
It has been proposed to prevent such cross-linking by the addition of chelating agents to the stimulation fluids. However, most of the commonlyavailable chelating agents are anionic in nature and therefore ineffective at low pH values, e.g. below pH4.
It has also been proposed to add reducing agents to the stimulation fluids, to reduce ferric ions to ferrous ions. While such a treatment would avoid sludge formation (ferrous ions would not cross-link the asphaltenic molecules) it leads to the deposit of ferrous sulphide, with consequent formation of scale and eventual blockage.
It has been unexpectedly found that the addition to an oil-extraction system of a phosphorus containing species results in the substantial prevention of sludge formation in the crude oil. It has also been found that certain phosphorus containing species can cause the breakdown of already-formed sludge in crude oil.
International Patent Publication No W004/104367 discloses a method for controlling the formation of ferric-ion-induced sludge in a process for the extraction of crude oil under acidic stimulation conditions. The method comprises the addition to the stimulation fluid or to the formation fluids of an effective amount of an organophosphorus species. The organophosphorus species of particular concern are alkyl-substituted phosphine oxides (THPO) and tetrakis(hydroxyalkyl)phosphonium salts (THPX) .
It has now been discovered that specific organophosphorus species are particularly beneficial in controlling the formation of ferric-ioninduced sludge in a process for the extraction of crude oil under acidic stimulation conditions.
Accordingly the present invention provides a method for controlling the formation of ferric-ion-induced sludge in a process for the extraction of crude oil under acidic stimulation conditions, said method comprises the addition to one or more of the stimulation fluid or the formation fluids of an effective amount of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate.
In the context of the present invention the phrase "formation fluids" takes the standard meaning known in the art of oil, water, gas or emulsion thereof.
Preferably the method substantially prevents the formation of the ferricion-induced sludge.
The alkylated phosphonic acid, or ester thereof, preferably includes an alkyl group comprising from 5 to 50 carbon atoms, more preferably from 6 to 20 carbon atoms and most preferably from 7 to 15 carbon atoms.
The alkyl group may comprise a straight or branched alkyl chain.
The alkylated phosphonic acid, or ester thereof, is most preferably selected from octyl phosphonic acid (OPA), octadecyl phosphonic acid, mono-methyl decyl phosphonate acid (MMDP) and generically similar compounds.
The aminophosphonate is preferably an aminomethylene phosphonate, most preferably a long chain alkyl aminomethylene phosphonate, such as one of the group available under the Trade Mark BRIQUEST and in particular BRIQUEST 281, which is (8-hydroxy octyl imino) bismethylene bisphosphonic acid.
Alkylated phosphonic acids, or esters thereof, and aminophosphonate species provide advantages over alkyl-substituted phosphine oxides and tetrakis(hydroxyalkyl)phosphonium salts. In particular the use of alkylated phosphonic acids, or esters thereof, and aminophosphonate species results in a faster phase separation of oil and acid layers and also reduces, or even substantially eliminates, the formation of precipitate in the acid layer.
Suitably, the stimulation fluid includes up to 28% by weight of an inorganic acid, for example hydrochloric acid. Other components present in the simulation fluid may include corrosion inhibitors, surfactants and other specialist additives.
The pH of the stimulation fluid or formation fluid is preferably 4 or less.
Preferably the temperature of the stimulation fluid or formation fluid is from 15 to 90CC, more preferably from 20 to 85 C and most preferably the temperature of the stimulation fluid or formation fluid is 80 oc. In use the stimulation fluid or formation fluid may be heated to the desired temperature. It has been observed that the stimulation fluid or formation fluid is stable at 80 C for about 14 days in the presence of the alkylated phosphonic acids, or esters thereof, or aminophosphonates used in the present invention.
The increased temperature of the stimulation fluid or formation fluid gives rise to almost instantaneous phase separation on addition of the alkylated phosphonic acids, or esters thereof, or the aminophosphonate species.
The alkylated phosphonic acid, or an ester thereof, or the aminophosphonate species is preferably added to the stimulation fluid or to the formation fluids in an amount of from 0.01% to 10% (by weight), preferably from 0.1 to 5% (by weight).
The alkylated phosphonic acid, or an ester thereof, or aminophosphonate species may be added to the stimulation fluid or to the formation fluids at any stage in the extraction process. It has been found that the formation of ferric-ion-induced sludge is substantially prevented, even when the alkylated phosphonic acid, or ester thereof, or the aminophosphonate species is pre-mixed with the stimulation fluid or formation fluids already containing ferric ions, resulting in rapid phaseseparation of fluid and oil.
It has further been found that the addition to one or both of the stimulation fluid or the formation fluid of 0.2% of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate species (by weight of oil) will control at least 5000 ppm of ferric ion. Furthermore the addition of 1% of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate species (by weight of oil) will control at least 10000 ppm of ferric ion.
Where the alkylated phosphonic acid, or an ester thereof, or aminophosphonate species, is contacted with a formation fluid, before contact with the stimulation fluid containing ferric ions it has been found that there is a substantial prevention of sludge-formation, with rapid phase-separation of fluid and oil.
It has further been found that the addition to the formation fluids of 1% of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate species (by weight of oil) will control at least 10000 ppm of ferric ion.
Further, it has been found that the alkylated phosphonic acid, or an ester thereof, or the aminophosphonate species can break down already- formed sludge in crude oil.
Thus, the present invention also provides the use of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate species to break down already-formed, ferric-ion-induced sludge in crude oil.
The alkylated phosphonic acid, or ester thereof, preferably has an alkyl chain length of from 5 to 50 carbon atoms, more preferably from 6 to 20 carbon atoms and most preferably from 7 to 15 carbon atoms. The alkyl group may comprise a straight or branched alkyl chain.
The alkylated phosphonic acid, or ester thereof, is most preferably selected from octyl phosphonic acid (OPA), octadecyl phosphonic acid, mono-methyl decyl phosphonic acid (MMDP) and generically similar compounds.
The aminophosphonate is preferably an aminomethylene phosphonate, most preferably a long chain alkyl aminomethylene phosphonate, such as one of the group available under the Trade Mark BRIQUEST and in particular BRIQUEST 281, which is (8-hydroxy octyl imino) bismethylene bisphosphonic acid.
The already-formed sludge may be exposed to the alkylated phosphonic acid, or an ester thereof, or the aminophosphonate species for a soaking period, suitable of between 6 and 96 hours, which enables existing sludge to be broken down and/or removed.
The present invention will be illustrated by way of the following Examples in connection with which: Figures 1 and 2 show two samples of Machar crude oil, one treated with a stimulation fluid at 800C and the other treated with OPA, as well as a stimulation fluid at 80 C, after 5 minutes has elapsed; and Figures 3 and 4 show two samples of Machar crude oil, one treated with OPA and a stimulation fluid at 80 C and the other treated with THPO and a stimulation fluid at 80 C after 3 hours has elapsed.
Example 1
Method A sample of a typical North Sea crude oil, Machar, was treated with 1% octyl phosphonic acid (OPA) solution (by weight of the oil). A stimulation fluid, which had been heated to 80 C and comprised 15% hydrochloric acid and contained up to l0000ppm ferric ions was then added.
A further sample of the same typical North Sea crude oil was used as a control sample and was also treated with the stimulation fluid as set out above heated to 80 C.
A yet further sample of the same typical North Sea crude oil was treated with 0.1% THPO (by weight of the oil) before treatment with the stimulation fluid as set out above heated to 80 C.
Results In the case of the OPA treated sample, separation of oil and acid occurred within 5 minutes.
In the case of the THPO treated sample, phase separation of oil and acid took over 1 hour to occur. Furthermore the sludge formed a solid interface between the oil and acid phases.
In the control sample a sludge, which mobilised on incubation at 80 C, formed within 5 minutes. The sludge remained as a solid interface between the oil and acid phases as time progressed.
It can be seen from Figures 1 and 2 that after 5 minutes the sample of Machar crude oil treated with OPA and a stimulation fluid (A) had separated to give an oil phase and an acid phase whereas there had been no separation of the control sample (B) into these phases.
In Figure 3 it can be seen that after 3 hours the sample of Machar crude oil treated with a stimulation fluid and OPA (C) had separated into an oil phase and an acid phase but the sample treated with THPO (D) was only just beginning to separate.
In Figure 4 it is clear that the sludge in the sample of crude oil treated with THPO (D) has formed a solid interface between the oil and acid phases that is not present in the sample treated with OPA (C).
Example 2
Method The same experiments detailed above were carried out but with the stimulation fluid being at room temperature when added.
Results The separations were seen to be slower with the stimulation fluid added at room temperature rather than at 800C. In the OPA treated system separation occurred within 30minutes, in THPO separation occurred within 2 hours, and the control sample set solid with sludge within 5 minutes.
Claims (20)
1. A method for controlling the formation of ferric-ion-induced sludge in a process for the extraction of crude oil under acidic stimulation conditions, said method comprising the addition to one or both of the stimulation fluid or the formation fluids of an effective amount of an alkylated phosphonic acid, or an ester thereof, or an aminophosphonate species.
2. A method according to Claim 1 wherein the alkylated phosphonic acid, or ester thereof, includes an alkyl group comprising from 5 to 50 carbon atoms.
3. A method according to Claim 1 or Claim 2 wherein the alkylated phosphonic acid, or ester thereof, includes an alkyl group comprising from 6 to 20 carbon atoms.
4. A method according to any of Claims 1 to 3 wherein the alkylated phosphonic acid, or ester thereof, includes an alkyl group comprising from 7 to 15 carbon atoms.
5. A method according to any preceding claim wherein the alkylated phosphonic acid, or ester thereof, is selected from octyl phosphonic acid (OPA), octadecyl phosphonic acid, mono-methyl decyl phosphonate acid (MMDP) and generically similar compounds.
6. A method according to Claim 1 wherein the aminophosphonate is an aminomethylene phosphonate.
7. A method according to any one of the preceding claims, in which the stimulation fluid includes up to 28% by weight of an inorganic acid.
8. A method according to Claim 7, in which the inorganic acid is hydrochloric acid.
9. A method according to any one of the preceding claims, in which the pH of the stimulation fluid or the formation fluids is 4 or less.
10. A method according to Claim 1, in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is added to the stimulation fluid or the formation fluids at any stage in the stimulation process.
11. A method according to any preceding claim in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is added to the stimulation fluid or the formation fluids and the stimulation fluid or the formation fluids is at or subsequently heated to 15 to 90 C.
12. A method according to any preceding claim in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is added to the stimulation fluid or the formation fluids and the stimulation fluid or the formation fluids is at or subsequently heated to 80 C.
13. A method according to Claim 1, in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is added to one or both of the stimulation fluid or the formation fluids at any stage in the stimulation or extraction process.
14. A method according to Claim 1 in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is contacted with the formation fluids before contact with the stimulation fluid.
15. A method according to Claim 1 in which the alkylated phosphonic acid, or ester thereof, or the aminophosphonate is contacted with the stimulation fluid before contact with the formation fluids.
16. A method according to any one of the preceding claims, in which the organophosphorus species is added to one or both of the stimulation fluid or the formation fluids in an amount of from 0.01% to 10% (by weight).
17. The use of an alkylated phosphonic acid, or ester thereof, or an aminophosphonate to break down already-formed, ferric-ion-induced sludge in crude oil.
18. Use according to Claim 17, in which the sludge is exposed to the alkylated phosphonic acid, or ester thereof, or the aminophosphonate for a soaking period of between 6 to 96 hours.
19. A method for controlling the formation of ferric-ion-induced sludge in a process for the extraction of crude oil under acidic stimulation conditions substantially as described herein and with reference to the
Examples.
20. The use of an alkylated phosphonic acid, or ester thereof, or an aminophosphonate to break down already-formed, ferric-ion-induced sludge in crude oil substantially as described herein and with reference to
the Examples.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0502762A GB2423099A (en) | 2005-02-10 | 2005-02-10 | Phosphorus containing species in sludge control |
| PCT/EP2006/001063 WO2006084662A1 (en) | 2005-02-10 | 2006-02-07 | Phosphorous-containing species for use in sludge control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0502762A GB2423099A (en) | 2005-02-10 | 2005-02-10 | Phosphorus containing species in sludge control |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0502762D0 GB0502762D0 (en) | 2005-03-16 |
| GB2423099A true GB2423099A (en) | 2006-08-16 |
Family
ID=34356091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0502762A Withdrawn GB2423099A (en) | 2005-02-10 | 2005-02-10 | Phosphorus containing species in sludge control |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2423099A (en) |
| WO (1) | WO2006084662A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077078A1 (en) | 2007-12-15 | 2009-06-25 | Clariant Finance (Bvi) Limited | Asphalt dispersers on the basis of phosphonic acids |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998030783A1 (en) * | 1997-01-13 | 1998-07-16 | Bp Chemicals Limited | A process and a formulation to inhibit scale in oil field production |
| WO2004018834A1 (en) * | 2002-08-20 | 2004-03-04 | Baker Hughes Incorporated | Method for controlled placement of oilfield chemicals and composition useful for practicing same |
| WO2004104367A1 (en) * | 2003-05-24 | 2004-12-02 | Rhodia Consumer Specialties Limited | Sludge control in crude oil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3511760A1 (en) * | 1985-03-30 | 1986-10-02 | Akzo Gmbh, 5600 Wuppertal | AGENT AGAINST FELLING AND DEPOSITING ASPHALTED AND THE LIKE |
| CA1278178C (en) * | 1989-01-04 | 1990-12-27 | Sylvia K. Pachla | Anti-sludging treatment |
| DE19828352A1 (en) * | 1998-06-25 | 1999-12-30 | Clariant Gmbh | Synergistic mixtures of phosphoric acid esters with carboxylic acids or carboxylic acid derivatives as asphaltene dispersants |
-
2005
- 2005-02-10 GB GB0502762A patent/GB2423099A/en not_active Withdrawn
-
2006
- 2006-02-07 WO PCT/EP2006/001063 patent/WO2006084662A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998030783A1 (en) * | 1997-01-13 | 1998-07-16 | Bp Chemicals Limited | A process and a formulation to inhibit scale in oil field production |
| WO2004018834A1 (en) * | 2002-08-20 | 2004-03-04 | Baker Hughes Incorporated | Method for controlled placement of oilfield chemicals and composition useful for practicing same |
| WO2004104367A1 (en) * | 2003-05-24 | 2004-12-02 | Rhodia Consumer Specialties Limited | Sludge control in crude oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077078A1 (en) | 2007-12-15 | 2009-06-25 | Clariant Finance (Bvi) Limited | Asphalt dispersers on the basis of phosphonic acids |
| DE102007060651B3 (en) * | 2007-12-15 | 2009-06-25 | Clariant International Limited | Asphaltene dispersants based on phosphonic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0502762D0 (en) | 2005-03-16 |
| WO2006084662A1 (en) | 2006-08-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |