WO2002042063A1 - Method for extending the useable life of a polyamide pipe liner during use in a water-oil-gas environment - Google Patents
Method for extending the useable life of a polyamide pipe liner during use in a water-oil-gas environment Download PDFInfo
- Publication number
- WO2002042063A1 WO2002042063A1 PCT/US2001/043837 US0143837W WO0242063A1 WO 2002042063 A1 WO2002042063 A1 WO 2002042063A1 US 0143837 W US0143837 W US 0143837W WO 0242063 A1 WO0242063 A1 WO 0242063A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- pipe
- sheath
- oil
- gas
- Prior art date
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 107
- 229920002647 polyamide Polymers 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002274 desiccant Substances 0.000 claims abstract description 14
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 9
- 230000003716 rejuvenation Effects 0.000 claims abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 230000004888 barrier function Effects 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002959 polymer blend Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 241000009298 Trigla lyra Species 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 10
- 238000012668 chain scission Methods 0.000 abstract description 9
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000011017 operating method Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
Definitions
- the invention pertains to polyamide pipe liners used for the transport of oil or gas, and, more particularly, to a method for extending the useable life of a polyamide pipe liner that is used in a water-oil-gas environment.
- Polyamide (PA) materials are used as liners for a gas-oil-water barrier in pipes used to transport gas, oil water and mixtures thereof.
- the normal practice in the industry is to extrude a nylon sheath in the shape of a continuous tube of a thickness ranging from several millimeters to several centimeters. This tube will be the principal barrier containing the fulid under flow.
- a sacrificial layer several millimeters thick is extruded as a layer to protect the principal layer from mechanical friction (i.e., wear as it rubs against an internal metal carcass). The metal carcass prevents collapse of the piper from the sub-sea environment.
- a sacrificial layer may also be placed outside the principal PA layer to prevent friction wear of the principal layer with outer metal windings used to contain the often high internal pressures of the pipe which can be over 100 atmospheres.
- Prior art also shows the measurement of the molecular weight of PA using witness coupons or taking small samples of the PA liner as a means for monitoring aging of the PA liner.
- Molecular weight has been shown to be correlated with the PA liner's performance mechanical properties. See, for example, U.S. Patent 5,614,683 which is herein incorporated by reference.
- the major aging process causing degradation of polyamide (PA) when used as a pipe liner for the transport of oil, gas, and/or water has been found to be the result of two competing processes.
- Figure 1 is a graph showing the deterioration of molecular weight of a polyamide 11 sample over time at various temperatures in a 100% water environment for a relatively high molecular weight sample (77,000);
- Figure 2 is a graph showing an increase in the molecular weight of a polyamide 11 sample over time at various temperatures in a 100% water environment for a relatively low molecular weight sample (14,000);
- Figure 3 is a graph showing changes in molecular weight for a relatively high molecular weight polyamide 11 sample over time in different environments (e.g., dry oil (1% acid, dry), and oil-acid-water with increasing percentages of acid) at 115°C);
- environments e.g., dry oil (1% acid, dry), and oil-acid-water with increasing percentages of acid
- Figure 4 is a graph showing the changes in molecular weight of over time for a polyamide 11 sample over time which incorporates polyethylene glycol;
- Figure 5 is a cross-sectional view of a pipe typically used to transport oil or gas from a sub sea environment
- Figure 6 is a cross-sectional view of a pipe typically used to transport oil or gas above ground.
- Figure 2 shows the change in molecular weight of a lower molecular weight sample at these same temperatures and in the same environment. That is, in both Figure 1 and 2, the samples were stored in 100% water. In Figure 1, the sample had a starting molecular weight of 77,000, and in Figure 2, the sample had a starting molecular weight of 14,000. Figure 2, in contrast to Figure 1, shows that the molecular weight is increasing. Together, Figures 1 and 2 show the existence of processes which involve both chain scission and chain recombination during aging in a water- hydrolysis environment.
- Figure 3 shows the change in molecular weight of a relatively high molecular weight polyamide 11 sample in an oil-acid- water environment. Figure 3 shows a much slower rate of decrease in the molecular weight when less acid- water is present. Figure 3 also shows in a dry oil environment, the molecular weight exhibits a small increase in its value over time.
- Figures 1-3 demonstrate that the molecular weight of a polyamide can either decrease or increase depending on the environment in which it is used. This is the basis for the method of extending the life expectancy of a pipe liner used in a water-oil-gas environment through manufacturing design and material modification or operating procedures during use, such as filling the pipe with a hot drying agent or hot dry oil. Decreasing the amount of water present in the polyamide at any given temperature will increase the relative rate of chain recombination or polymerization and will decrease the relative rate of chain scission caused by hydrolysis. Decreasing the amount of water present in the polyamide tube liner can be controlled by several methods.
- One method involves constructing an inner sheath inside the principal piper liner which significantly reduces the diffusion of water in the polyamide barrier.
- suitable materials include fluorinated polymers such as tetrafluorinated polyethylene or polyvinyldifluoride.
- a second method involves modification to the polyamide structure which reduces water solubility in the polyamide. Examples of chemical modifications including adding moieties which reduce the concentration of water or solubility through copolymer, block polymer, graft polymer, polymer blends, or adding bulky or hydrophobic groups near the amide bond to create a modified polyamide chain.
- a third method involves use of additives in the pipe flow streams which complex and/or bind up the free water so that it does not diffuse into the polyamide sheath.
- a fourth method involves placing a drying agent in the pipe which reduces the water content in the polyamide sheath, and then allowing the pipe to heat up, as for example, by placing a hot dry oil in the pipe so the recombination rate can be made to exceed the rate of chain scission and the molecular weight of the polyamide (e.g., polyamide 11) can be increased.
- a drying agent such as, but not limited to sodium sulfate, calcium chloride, and magnesium sulfate.
- hot oil or hot oil with another liquid plus a dessicant such as sodium sulfate, calcium chloride, magnesium sulfate could be used to fill the pipe, with the desiccant serving the function of reducing or eliminating water from the pipe liner.
- a dessicant such as sodium sulfate, calcium chloride, magnesium sulfate
- Figure 4 shows that when the polyamide is exposed to ethylene glycol, a substance which is both a chain extender which can react with two polyamide chains tying them together with esterification, and also that can tie up water, the rate of degradation is decreased.
- a chain extender and/or water complexing agent such as ethylene glycol
- Figures 5 and 6 illustrate practical implementations of the claimed invention in pipes typically used to transport oil or gas in a sub sea environment or over ground, respectively.
- Figure 5 there is an inner metal carcass 10 and an outer metal sheath 12.
- Figure 6 there is no inner metal carcass, but there is an outer metal sheath 12.
- a sheath 14 impermeable to water, but not gas or oil is adhered to the inner surface of the polyamide barrier layer 16.
- This sheath 14 can be extruded separately or simultaneously with the polyamide barrier layer 16.
- the sheath 14 serves the function of reducing the permeation of water in the fluid flow within the pipe into the polyamide barrier layer.
- suitable sheath materials include but are not limited to polyvinylchloride (PVC), polyvinyldifluoride
- the polyamide barrier layer 16 acts as a barrier to the gas or oil being transported by the pipe.
- the sheath 14 and barrier layer 16 can each be on the order of several millimeters to several centimeters thick. In another embodiment of the invention the sheath 14 is eliminated.
- the polyamide barrier layer 16 is altered to be more resistant to water permeation, thereby reducing hydrolysis of the chemical backbone.
- a desiccant such as sodium sulfate, magnesium sulfate, or calcium chloride is incorporated into the polyamide barrier layer 16 during extrusion.
- the quantity of desiccant would be less than 10% by weight of the extruded material.
- the desiccant in the barrier layer 16 would bind up the water which permeates from the gas or oil into the barrier layer, and thereby reduce chain scission.
- the polyamide barrier layer 16 is a constructed as a copolymer such as a graft copolymer wherein hydrophobic side chains are covalently bonded to a backbone of a polyamide, a block copolymer wherein hydrophobic polymer chains are joined with the polyamide (e.g., alternating sections of the polymer would include polyamide and hydrophobic polymers), and polymer blends which include mixtures of hydrophobic polymers and polyamides.
- hydrophobic moieties such as halogens can be attached directly to the polyamide or to chains which are grafted to the polyamide.
- polymers such as PVC, PVDF, and PTFE might be used.
- a piece of aged polyamide liner having a molecular weight between 24,000 and 28,000 was placed in a dry hot air environment for six days. At 24,000 to 28,000 molecular weight, the polyamide liner is generally replaced since at this molecular weight it is no longer elastic and becomes brittle. After six days at 100°C, the polyamide liner material was rejuvenated to a level of 35,000 molecular weight. A similar piece of aged polyamide liner was treated for six days at 150°C and was rejuvenated to a higher molecular weight level. The high temperature may be driving off water that permeated into the polyamide as steam.
- the life expectancy of the polyamide barrier layer may be increased by periodic heat treatment such that moisture is driven out.
- hot air can be directed through the pipe to rejuvenate the polyamide barrier layer, or a hot dry oil or gas at a temperature sufficient to drive out water can be directed though the pipe, or another dry liquid or a combination of gas or oil and another dry liquid at a temperature sufficient to drive out water can be directed through the pipe.
- a desiccant or chain extender could be incorporated into the hot dry liquid directed through the pipe.
- the drying fluid will be of a sufficiently high heat capacity that it will allow adequate heating over the entire length of the polyamide liner when the fluid is injected at one end of the pipe (i.e., it will remain sufficiently warm to drive out water when it reaches the other end of the pipe).
- the pipe itself could include heating devices or hot air delivery devices used to heat a drying fluid and the polyamide material on a periodic basis.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0115681-0A BR0115681A (en) | 2000-11-24 | 2001-11-23 | Oil or gas conveying pipe, method for extending the life of a polyamide barrier layer in an oil or gas conveying pipe, method for rejuvenating a polyamide barrier layer used in a conveying pipe or gas, and method for extending the life expectancy of a polyamide material |
AU1672202A AU1672202A (en) | 2000-11-24 | 2001-11-23 | Method for extending the useable life of a polyamide pipe liner during use in a water-oil-gas environment |
EP01997207A EP1355779A4 (en) | 2000-11-24 | 2001-11-23 | Method for extending the useable life of a polyamide pipe liner during use in a water-oil-gas environment |
US10/432,525 US20040045620A1 (en) | 2001-11-23 | 2001-11-23 | Method for extending the useable life of a polyamide pipe liner during use in a water-oil gas environment |
NO20032296A NO20032296L (en) | 2000-11-24 | 2003-05-21 | Method for Extending the Life of a Polyamide Stir Liner Using in a Water-Oil-Gas Environment |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25258300P | 2000-11-24 | 2000-11-24 | |
US60/252,583 | 2000-11-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002042063A1 true WO2002042063A1 (en) | 2002-05-30 |
Family
ID=22956624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/043837 WO2002042063A1 (en) | 2000-11-24 | 2001-11-23 | Method for extending the useable life of a polyamide pipe liner during use in a water-oil-gas environment |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1355779A4 (en) |
AU (1) | AU1672202A (en) |
NO (1) | NO20032296L (en) |
WO (1) | WO2002042063A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109595402A (en) * | 2018-12-10 | 2019-04-09 | 运城学院 | A kind of chemical industry equipment pipeline and its pipeline processing technique |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5038833A (en) * | 1985-03-22 | 1991-08-13 | Technoform Caprano+Brunnhofer Kg | Fuel line for fixed-length vehicle installation |
US5152323A (en) * | 1988-11-22 | 1992-10-06 | Allied Tube & Conduit Corporation | Plastic-lined pipe |
US5339867A (en) * | 1991-12-12 | 1994-08-23 | Itt Corporation | Composite metal tube and method of making the same |
US5500263A (en) * | 1993-04-02 | 1996-03-19 | Huels Aktiengesellschaft | Multilayer plastic pipe |
US6110550A (en) * | 1996-11-22 | 2000-08-29 | Institut Francais Du Petrole | Limited permeability sheath and application to pressure pipes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT222865Z2 (en) * | 1991-08-02 | 1995-05-08 | Mazzer Materie Plastiche | ANTI-STATIC PLASTIC TUBE FOR CONVEYING EVAPORABLE AND FLAMMABLE SUBSTANCES, IN PARTICULAR FOR VEHICLE FUEL SUPPLY SYSTEMS |
DE19823585A1 (en) * | 1998-05-27 | 1999-12-02 | Basf Ag | Composite element containing polyisocyanate polyaddition products |
DE29816278U1 (en) * | 1998-09-10 | 1998-12-10 | PIOFLEX Kunststoff in Form GmbH & Co., 79211 Denzlingen | Plastic hose made up of several concentric layers |
-
2001
- 2001-11-23 AU AU1672202A patent/AU1672202A/en active Pending
- 2001-11-23 EP EP01997207A patent/EP1355779A4/en not_active Withdrawn
- 2001-11-23 WO PCT/US2001/043837 patent/WO2002042063A1/en not_active Application Discontinuation
-
2003
- 2003-05-21 NO NO20032296A patent/NO20032296L/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5038833A (en) * | 1985-03-22 | 1991-08-13 | Technoform Caprano+Brunnhofer Kg | Fuel line for fixed-length vehicle installation |
US5152323A (en) * | 1988-11-22 | 1992-10-06 | Allied Tube & Conduit Corporation | Plastic-lined pipe |
US5339867A (en) * | 1991-12-12 | 1994-08-23 | Itt Corporation | Composite metal tube and method of making the same |
US5500263A (en) * | 1993-04-02 | 1996-03-19 | Huels Aktiengesellschaft | Multilayer plastic pipe |
US6110550A (en) * | 1996-11-22 | 2000-08-29 | Institut Francais Du Petrole | Limited permeability sheath and application to pressure pipes |
Non-Patent Citations (1)
Title |
---|
See also references of EP1355779A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109595402A (en) * | 2018-12-10 | 2019-04-09 | 运城学院 | A kind of chemical industry equipment pipeline and its pipeline processing technique |
Also Published As
Publication number | Publication date |
---|---|
NO20032296D0 (en) | 2003-05-21 |
EP1355779A4 (en) | 2005-03-09 |
NO20032296L (en) | 2003-05-21 |
AU1672202A (en) | 2002-06-03 |
EP1355779A1 (en) | 2003-10-29 |
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